Acs Chemrev 1c00836

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org/CR Review
Transition-Metal-Catalyzed C−S, C−Se, and C−Te Bond Formations

via Cross-Coupling and Atom-Economic Addition Reactions.
Achievements and Challenges
Irina P. Beletskaya* and Valentine P. Ananikov*
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ABSTRACT: In the present review, we discuss recent progress in the field of C−Z bond
formation reactions (Z = S, Se, Te) catalyzed by transition metals. Two complementary
methodologies are considered�catalytic cross-coupling reactions and catalytic addition
reactions. The development of advanced catalytic systems is aimed at improved catalyst
efficiency, reduced catalyst loading, better cost efficiency, environmental concerns, and
higher selectivity and yields. The important rise of research efforts in sustainability and green
chemistry areas is critically assessed. The paramount role of mechanistic studies in the
development of a new generation of catalytic systems is addressed, and the key
achievements, problems, and challenges are summarized for this field.
CONTENTS 4.2.2. Chan−Lam Coupling Reaction with the

Formation of the C(sp2)−S Bond 16184
1. Introduction 16111 4.2.3. C−H Functionalization 16197
2. Development of Advanced Catalytic Systems 16115 4.3. Other Metals in C−Z Cross-Coupling Re-
2.1. Reducing Waste and Improving the Effi- actions 16213
ciency of Utilization of the Atom-Economy 4.3.1. Nickel 16214
Concept 16115 4.3.2. Cobalt 16224
2.2. Reducing the Cost of Catalysts and Sustain- 4.3.3. Iron 16230
ability Issues 16116 4.3.4. Ruthenium 16236
2.3. Toxicity of Metal Catalysts and Environ- 4.3.5. Iridium 16237
mental Concerns 16116 4.3.6. Rhodium 16238
3. Mechanistic Understanding of Catalytic Systems 16118 4.3.7. Silver 16240
3.1. General Mechanistic Framework of C−Z 4.3.8. Molybdenum 16242
Cross-Coupling and Z−H/Z−Z Addition 4.3.9. Manganese 16242
Reactions 16118 4.3.10. Zirconium, Bismuth, and Indium 16244
3.2. Nature of Catalytically Active Species 16120 4.3.11. Lanthanides 16244
3.3. Difficulties in Catalyst Recycling 16121 4.4. Photoredox Initiation of Reactions Cata-
4. Catalytic Cross-Coupling Reactions (Z = S, Se, Te) 16122 lyzed by Transition Metal Complexes 16244
4.1. Palladium-Catalyzed Transformations 16122 5. Catalytic Z−H Bond Addition Reactions (Z = S,
4.1.1. Cross-Coupling with Thiols 16122 Se, Te) 16246
4.1.2. Sulfur Sources Other than Thiols 16126
4.1.3. Heterogeneous Palladium-Catalyzed S-
Cross-Coupling 16134
4.1.4. Pd(II)-Catalyzed Oxidative Reactions 16136 Received: September 28, 2021
4.1.5. C−H Functionalization 16137 Published: September 16, 2022
4.2. Copper-Catalyzed Transformations 16143
4.2.1. Modern Ullmann Chemistry 16143
© 2022 American Chemical Society https://doi.org/10.1021/acs.chemrev.1c00836

16110 Chem. Rev. 2022, 122, 16110−16293
Chemical Reviews pubs.acs.org/CR Review
5.1. Palladium-Catalyzed Transformations 16246 Ullmann and Goldberg. However, this is a different
5.2. Rhodium and Iridium-Catalyzed Transfor- chemistry�this is the new Ullmann, which has become
mations 16249 possible due to the usage of new types of ligands. Replacing
5.3. Copper-Catalyzed Transformations 16252 palladium with cheaper and more easily available copper makes
5.4. Other Metals As Catalysts 16252 this chemistry more affordable and practically efficient. Finding
5.4.1. Nickel 16252 replacements for (currently highly expansive) noble metals also
5.4.2. Cobalt 16253 provides an outstanding driving force for catalysis with nickel,
5.4.3. Gold 16253 cobalt, iron, and many other metals.
5.4.4. Zinc 16254 Sometimes the topic is also presented as a replacement of
5.4.5. Iron 16254 toxic metals (i.e., Pd, etc.) with “less toxic” and environ-
5.4.6. Indium 16254 mentally safe alternatives (i.e., Ni, Cu, etc.). Although it is a
5.4.7. Manganese 16254 widespread assumption, critical analysis does not find it as
5.4.8. Cerium 16254 obvious as it may seen. This topic will be discussed in a
5.4.9. Ruthenium 16254 dedicated section of the present review.
5.4.10. Scandium 16254 For a long time, thiols (RSH) were considered the best
5.5. Photoredox Processes in Z−H Bond Addi- possible reagent for cross-coupling. Currently, a range of thiol
tion Involving Transition Metal Complexes 16254 substitutes and surrogates have been widened significantly to
6. Catalytic Z−Z and C−Z Bond Addition Reactions replace older compounds, which, because of their smell and
(Z = S, Se, Te) 16256 toxicity, have hindered the broad application of cross-coupling
6.1. Palladium-Catalyzed Transformations 16256 for the synthesis of sulfides.
6.2. Nickel-Catalyzed Transformations 16258 In addition to Ullmann cross-coupling, copper has a special
6.3. Rhodium-Catalyzed Transformations 16260 field of application, that is, the Chan−Evans−Lam reaction
6.4. Copper-Catalyzed Transformations 16260 (the Chan−Lam reaction for sulfur), where ligands are not
6.5. Gold-Catalyzed Transformations 16261 required. It should be noted that the transition from palladium
6.6. Iron-Catalyzed Transformations 16262 to copper was a considerable gift for chemists that allowed the
6.7. Rhenium-Catalyzed Transformations 16262 replacement of phosphine ligands with amines and other “safe”
7. Comparison of Research Trends over the Recent compounds. Equally important, the field of C−H functional-
Decade 16262 ization is also a subject for copper catalysis, although in this
8. Conclusions 16263 case metalation is coupled with oxidation.
Achievements 16263 Despite the obvious practical importance of Cu-catalyzed
Problems 16264 reactions, the replacement of palladium with copper raises the
Challenges 16264 issue of the reaction mechanism and deprives scientists of the
Author Information 16265 possibility of using powerful tools, such as NMR. A new wave
Corresponding Authors 16265 of mechanistic studies is currently under way with many novel
Notes 16265 findings. However, real insight into the nature of many
Biographies 16265 catalytic cross-coupling and addition reactions is expected to
Acknowledgments 16265 be made in the future.
References 16265 The transition of synthetic organic chemistry from
homogeneous catalysis to heterogenized catalysis, then to
heterogeneous catalysis, and finally to nanocatalysis has also
1. INTRODUCTION been evident in the considered field. In a number of C−Z bond
This review is dedicated to the synthesis of organochalcogen formation reactions, the application of nanosized metal-
compounds of sulfur, selenium, and tellurium via cross- containing particles (metal nanoparticles, metal oxide nano-
coupling (substitution) and addition reactions catalyzed by particles, “nanosalts”, hybrid nanostructures, etc.) has become
transition metals. Mostly, compounds with C(sp2)−Z bonds popular despite issues with mechanistic understanding.
(Z = S, Se, Te) are obtained using these synthetic Most importantly, the significance of organochalcogen
methodologies, although some examples of C(sp3)−Z and compounds has dramatically increased in recent years. Many
C(sp)−Z bond formations are also known and discussed. A sulfur compounds demonstrate tunable biological activity, and
previous version of the review on catalytic C−Z bond the C(sp2)−SR motif is found in many natural compounds.
formation was published in 2011.1 Here, we do not repeat For example, thioethers are an important class of organic
the discussions presented previously; rather, a new develop- compounds that have applications in biological chemistry,
ment that appeared after 2011 is the focus of the present design of drugs, organic synthesis, and material chemistry.2−20
review. A brief illustrative overview of a few selected examples of
In the 20th century, palladium catalysis was considered a chalcogen-based compounds studied in the areas of drug
revolution in synthetic chemistry. Indeed, Pd-catalyzed trans- design, biologically active compounds, agrochemicals, and
formations played a key role in designing synthetic procedures materials chemistry is provided (Table 1). Various aspects have
for carbon−chalcogen bond formation via addition and cross- been considered in excellent reviews dedicated to a specific
coupling reactions.1 This was in full agreement with the topic.1,5,21−73
tendencies observed in carbon−carbon and other carbon− In general, organosulfur compounds constitute approx-
heteroatom bond formation reactions. Since then, chemistry imately 20% of all drugs approved by the FDA.57,74 Six
has changed profoundly, and the current field has also been sulfur-based functional groups are listed among the most
transformed. Accordingly, counterrevolution has begun�the frequent functionalities available in bioactive molecules
catalysis returns to copper compounds and the chemistry of discussed in the medicinal chemistry context.75
16111 https://doi.org/10.1021/acs.chemrev.1c00836
Chem. Rev. 2022, 122, 16110−16293
Table 1. Examples of Useful Compounds Containing C−S or C−Se Bonds
Chem. Rev. 2022, 122, 16110−16293
Table 1. continued
Chem. Rev. 2022, 122, 16110−16293
Table 1. continued
Of course, it should be mentioned that noncatalytic methods are involved in organic synthesis. Just a few representative
were successfully used for a long time for the preparation of examples may be mentioned in this regard.65,67,69,70,76−82 We
organosulfur and other organochalcogen compounds and still do not consider noncatalytic reactions in this review since we
Chem. Rev. 2022, 122, 16110−16293
Scheme 1. Comparative Analysis of Cross-Coupling (A−C) and Addition (D−E) Methodologies Using Simplified Model
Reactions
focus only on newly developed catalytic methodologies, which the present review, the amount of waste generated by
demonstrate a number of advantages and future potential. chromatography can be even larger compared to the amount
generated by the reaction itself.116 The advantages provided by
2. DEVELOPMENT OF ADVANCED CATALYTIC the atom-economic nature of the addition methodology are
SYSTEMS totally diminished by the purification procedure if the addition
reaction is followed by chromatography or a similar waste-
Two principally different concepts are currently utilized for the
abundant procedure.
efficient formation of carbon−heteroatom bonds in catalytic
In addition to the processing of reaction mixtures and
reactions: (i) cross-coupling methodology and (ii) addition
product purification, the use of an excess of starting material or
reaction methodology. The principal difference, which is
a reagent is also a negative factor for the overall green metrics
important to highlight, is not only in the reaction mechanisms
of the reaction. Analysis of the literature covered in the present
and conditions. Conceptually, the difference is in the accessible
review shows that a 1.2−2-fold excess of starting materials is
range of conversion efficiency of a chemical process and
often involved in cross-coupling and addition procedures to
amounts of generated waste.113−115
accelerate the reaction and/or to achieve complete conversion
The cross-coupling reaction, by its nature, is a substitution
of one of the components of the reaction. A nonstoichiometric
process, where halogen X is substituted by a heteroatom-
amount of base (sometimes a rather large excess) is also not
centered molecular fragment (Scheme 1A). In a typical case,
uncommon. An excess of the reagents and starting materials
the formation of an HX molecule as a byproduct is
remains as waste and gradually decreases the overall green
unavoidable. Moreover, usually 1 equiv of base is consumed,
and the base·HX molecule is released as waste (Scheme 1B,C). metrics. Recycling of solvents and unreacted reagents may help
Addition reactions are characterized by 100% atom to improve the metrics but is rarely employed in practice.
economy�all reagents are combined into the product Of course, we should emphasize that this is not a new issue
(Scheme 1D,E). This is an idealized picture, which shows that appeared recently. Instead, it is a long-standing problem
that addition reactions can be completely atom-economic by discussed many times in the literature. We want to critically
design. comment that little progress was achieved in this direction.
As an illustration, optimization of the reaction conditions
2.1. Reducing Waste and Improving the Efficiency of made it possible to reduce the amount of waste from cEF =
Utilization of the Atom-Economy Concept 94.1−1672.0 g/g to as small as cEF = 0.8−7.6 g/g in the
Complete atom efficiency and the absence of byproducts in reaction involving vinyl sulfides.116 This example suggests that
addition reactions are important factors from the point of view a large potential remains unused, and a new wave of research
of the development of green chemical processes. The should appear focusing on the real efficiency of product
introductions of many research articles dealing with addition synthesis.
reactions very well highlight this topic and indicate the absence Reducing the waste during product purification and avoiding
of waste as a key motivation. nonstoichiometric amounts of reagents are equally important
However, critical analysis of the literature devoted to for both types of considered methodologies�cross-coupling
catalytic addition reactions shows a major obstacle in the and addition reactions. Optimization of reactions in terms of
separation procedures used. Most often, chromatography or green metrics and careful solvent selection117 will substantially
extraction followed by chromatography is utilized for product contribute to the development of a new generation of eco-
separation and purification. For the methodology considered in friendly catalytic procedures.
Chem. Rev. 2022, 122, 16110−16293
Figure 1. (A) Trends for the palladium (green) and gold (yellow) prices. (B) Trend for the rhodium price (in USD/t oz.). Data source: matthey.
com.
It should be pointed out that in Sections 2 and 2.1, the However, critical analysis of the literature does not confirm
catalytic methodologies were considered only in a very such a general trend.118 In fact, it is one of the myths in the
simplified manner to illustrate the main differences. Particular public perception of the toxicity of metal compounds.119
illustrative reactions were taken as examples. Of course, a more As an illustrative example, we may consider LD50 values�
detailed comparison including chemical components (solvents, the median lethal dose or the dose which kills 50% of members
auxiliaries, etc.) and reaction performance (yields, selectivities, of a tested population (the smaller the value, the higher the
etc.) may be required for a precise analysis. toxicity; often measured on mice and rats). The values for
2.2. Reducing the Cost of Catalysts and Sustainability CuCl2 available in the literature119 are LD50 = 140−584 mg ×
Issues kg−1 and indicate much higher toxicity than the values reported
for PtCl2, LD50 = 3423 mg × kg−1.119 The toxicity of nickel
The cost of a catalyst is an important issue for industrial
applications and for widespread use in research. Rhodium and complexes may be higher than that of palladium and
palladium catalysts are often involved in C−S and C−Se bond platinum.118
formation reactions. A dramatic increase in the cost of noble The toxicity of Ni, Cu, and Co complexes was evaluated and
metals is very impressive for palladium, which became more showed substantial toxic and harmful effects.120−127 The
expansive than gold (Figure 1). The price for rhodium metal toxicity and biological impact of Pd, Pt, and Au complexes
also increased and still holds an impressive cost (Figure 1). and nanoparticles were also evaluated.128−130 However,
Such high prices and dynamics in their change urgently currently, it is not possible to define a universal trend since
require the development of alternative catalytic systems based each metal or even a particular metal compound may possess a
on cheap and easily available metals, such as Ni, Cu, Co, etc. specific activity.
The trend is clearly reflected in the number of publications in The relative toxicity scale may be described from extremely
recent decades and the rapid growth in the development of toxic to relatively harmless based on LD50 values (Figure 2). As
new catalytic systems using cheap metal catalysts. an example, the toxicity of simple chromium compounds,
In addition to the cost-efficiency issue, sustainability is a very depending on the metal oxidation state and ligands, may span a
important factor influencing metal selection for catalytic large range from relatively harmless (Cr2O3, LD50 > 15000 mg
systems. Metals such as Pd and Rh are very limited in the × kg−1) to moderately toxic (CrO3, LD50 = 52 mg × kg−1),
amount available on Earth, and their use in catalysis
unfortunately leads to incomplete recovery and spreading in
the environment as traces (e.g., traces in products, byproducts,
solvents, etc.). The recovery of trace metals after they spread in
the environment is a hardly achievable or enormously
expansive task. Thus, future generations may face a critical
shortage of noble metals if the sustainability issue is not
currently taken into account.
2.3. Toxicity of Metal Catalysts and Environmental
Concerns
A persistent belief in the field of catalysis and organic synthesis Figure 2. Relative toxicity ranges for metal compounds based on LD50
describes heavy-metal-based catalysts (Pd, Pt, Au, etc.) as toxic values. Adapted with permission from ref 119. Copyright 2017
and light-metal-based catalysts (Ni, Cu, Co, etc.) as less toxic. American Chemical Society.
Chem. Rev. 2022, 122, 16110−16293
with the other compounds in between (Figure 3).119 Notably, reveal potential biological activity. The toxicity of metal
both chromium chloride salts LD50 = 440 and 1870 mg × kg−1 complexes strongly depends on the oxidation state, ligands,
solubility, stability in water, interaction with other components
in the environment, etc. A substantial part of the overall
toxicity of a catalyst may originate from the ligands, as
sometimes the toxicity of ligands may exceed those of the
metal component itself. As an illustrative example, the toxicity
of many transition metal salts does not systematically exceed
the toxicity of solvents and some organic/organometallic
molecules (Figure 4).
In addition to the direct influence on humans, contami-
Figure 3. Acute toxicity of various chromium compounds (the color nation by transition metal pollutants raises important environ-
range is defined in Figure 2). Adapted with permission from ref 119. mental concerns. Metal species affect microorganisms, plants,
Copyright 2017 American Chemical Society. and several other components of ecosystems.131−135 Recently,
the evaluation of the phytotoxicity and cytotoxicity of
(CrCl2 and CrCl3, Figure 3) appear to be more toxic than industrial catalyst components (Fe, Cu, Ni, Rh, and Pd) has
“heavy-metal” platinum chloride LD50 = 3423 mg × kg−1.119 revealed an extraordinarily high lethal toxicity of rhodium(III)
Indeed, there is no such term as general toxicity, and each salt in terrestrial plants.131 Such studies highlight one more
particular metal complex or catalyst should be evaluated to important note concerning the toxic effect of metal compounds
Figure 4. Overview of the toxicity of common solvents, organic compounds, organometallic compounds, and metal salts. LD50 (oral rat, mg × kg−1)
values are shown on a logarithmic scale, with a color code as defined in Figure 2. Adapted with permission from ref 119. Copyright 2017 American
Chemical Society.
Chem. Rev. 2022, 122, 16110−16293
on the environment. Rapidly appearing toxic effects can be 3.1. General Mechanistic Framework of C−Z
estimated or predicted based on biological activity measure- Cross-Coupling and Z−H/Z−Z Addition Reactions
ments. However, it is not yet possible to predict after-effects, Mechanisms of catalytic cross-coupling reactions (see refs in
which may come after a significant amount of time. Although the Introduction) and addition reactions55,136−139 were
metals such as Ni, Cu, Co, etc. may possess a highly rapid toxic extensively reviewed earlier, and these discussions will not be
effect, living organisms have been in systematic contact with repeated here. In the present section, we outline a basic
these metals over a long historical period of time and may mechanistic framework for understanding a general concept of
develop a protection system to reduce after-effects. In contrast, the catalytic processes discussed in the sections below.
contact with metals such as Pd, Rh, Pt, etc. is the result of In a classical case, the cross-coupling reaction typically
human activity, and living organisms may not have involves an aryl halide (RX, X = I, Br, Cl) and thiol (RZH, Z =
evolutionarily developed protective mechanisms against these S) or a thiolate (RZM′, Z = S) as well as corresponding
compounds (see ref 131 for a discussion). Thus, a warning selenium or tellurium derivatives (Z = Se, Te). The main target
message should be noted, and dedicated studies should be is usually to achieve high catalyst activity in terms of large
performed. turnover number (TON) and turnover frequency (TOF)
Overall, studies dealing with the toxicity of metal catalysts values. A more active catalyst makes it possible to carry out the
and environmental concerns are currently at the beginning reaction at lower temperatures and increase functional group
stage, and the accumulation of more detailed knowledge is tolerance. Another advantage of high-performance catalysts is
urgently needed in the near future. the possibility of decreasing metal loadings to increase cost
Concerning the discussion in Section 2, although we efficiency and decrease the amount of waste.
presented only a very brief and noncomprehensive consid- In addition to efficiency goals, achieving reagent diversity is
eration of the issue, the following topics should be emphasized. currently a fascinating target. Different electrophilic compo-
In many publications in the title area, the aims were declared nents (RX) and an amazing number of nucleophilic
to improve atom economy, decrease the amounts of wastes, components (R′Z−) were successfully involved in cross-
and reduce toxicity, among other similar goals. However, no coupling using newly developed catalytic systems. Various
surrogates of thiols and selenols were used as starting materials
quantitative assessment of the metrics or biological activity was
for C−Z bond formation. Overall, these research endeavors
provided, which may lead to unjustified or even erroneous
have substantially contributed to the tremendous development
conclusions. Quantitative assessment is extremely rare (despite
of this field in the past decade.
declarative goals), and we consider it important to stimulate a A general mechanism of the catalytic cross-coupling
broader discussion on the subject based on calculated metrics. reactions starts with the activation of the initial catalyst (also
called the precatalyst), followed by entering the catalytic cycle
3. MECHANISTIC UNDERSTANDING OF CATALYTIC (Figure 5). Precatalyst activation is an important stage, which
SYSTEMS
In this section, we briefly discuss a few general mechanistic
frameworks of catalytic cycles and important intermediates. Of
course, it is a brief overview only since it is not possible to
summarize all possible options for the diversity of procedures
developed for C−Z bond formation reactions.
Several challenges in the mechanistic description of the
described catalytic reactions were not resolved yet. Particularly,
the catalytic process for C−Z bond formation via the cross-
coupling methodology and via the Z−H/Z−Z bond addition
methodology involves the same catalyst precursors, while
catalytically active centers may be substantially different. In
both methodologies, several synthetically relevant catalytic
transformations can be carried out using simple metal salts, for
example, Pd(OAc)2 and Ni(acac)2. Transition metal com-
plexes with phosphine and N-heterocyclic carbene (NHC)
ligands are other examples of catalysts equally important for
both methodologies. Common intermediates and an interplay
between homogeneous and heterogeneous catalytic systems
are amazing features of catalytic chemistry discussed in the Figure 5. C−Z cross-coupling reaction and a general catalytic cycle.
present review.
In addition to general mechanisms, a few representative
examples were also selected from the corresponding studies. is typically based on ligand coordination/replacement and
Several mechanistic schemes remain as “assumed” or metal reduction. Simple metal salts are often used as
“suggested”, which suggests further investigations in the future. precatalysts with the active form of a catalyst assembled in
We warn the readers to critically evaluate the mechanisms, and situ under catalytic conditions.
the assumptions presented should not be simply taken for The catalytic cycle starts with the oxidative addition of RX,
granted from one reaction to another. Even subtle changes in followed by coordination and transmetalation of the R′Z−
reaction conditions can have a noticeable effect on the component (Figure 5). C−Z reductive elimination creates the
catalytically active species and reaction mechanisms. product, and the cycle is completed after product release via
Chem. Rev. 2022, 122, 16110−16293
dissociation. Of course, this is a general scheme reflecting one representative example, catalytic cycles involving alkyne
of the possibilities. Other routes and combinations of insertion into the M−Z′ bond (Figure 6B) or insertion into
elementary steps may be involved following a general the M−H bond (Figure 6C), followed by C−H or C-Z
framework of powerful cross-coupling methodology. reductive elimination, should be mentioned. The particular
In general, Z−H bond addition to a multiple bond may reaction route can be controlled by the selection of metal and
result in the formation of different products depending on ligands.
regioselectivity (Figure 6A). Typically, the Z−H bond addition The two catalytic cycles shown (Figure 6B and C) involve
the metal center in two oxidation states (for example, M(0)/
M(II) for Ni and Pd or M(I)/M(III) for Rh). However, the
flexibility of the addition reaction allows the catalytic cycle to
be completed without the necessary change in the oxidation
state. In such a case, protonolysis is involved as a product
formation stage rather than reductive elimination (Figure 6D).
Such a mechanism may be involved in M/NHC catalytic
systems, oligomeric [M(ZR′)n]m catalysts and nanoparticles, as
well as some other cases.
Activation of a multiple C−C bond coordinated to the metal
center is a powerful tool that opens versatile possibilities in the
realization of catalytic reactions. As exemplified for Pd
complexes, either nucleophilic attack or insertion pathways
may take place (Figure 7). In the case of both pathways,
different products are accessible depending on the alkyne
orientation and the resulting regioselectivity of the process.
Achieving the desired Markovnikov/anti-Markovnikov selec-
tivity is one of the most interesting goals in the field. In the
present section, the catalytic cycles are depicted using alkyne
molecules as examples. Other catalytic procedures may also
involve different types of unsaturated molecules (alkenes,
dienes, etc.) with multiple bond activation by a metal center
and functionalization by attached chalcogen functional groups.
General mechanistic features of the insertion step were
discussed earlier,141 and a recent computational molecular
dynamics study140 revealed intrinsic atomic-scale details of this
step.
An important difference between the cross-coupling and
addition reaction methodologies should be mentioned. As a
general case, the components of the cross-coupling reaction do
not react with each other without a catalyst (except in some
specific cases). However, this is not the case for the addition
reaction, where two components can readily react without a
catalyst due to free radical or nucleophilic side reactions. Side
reactions decrease the overall selectivity of the addition process
and may lead to a mixture of Markovnikov, Z-anti-
Markovnikov, and E-anti-Markovnikov isomers. This is an
important issue, which requires thorough optimization of the
reaction conditions to obtain a high overall selectivity.
The catalytic Z−Z bond addition reaction follows a similar
Figure 6. Model catalytic cycles of Z−H bond addition using alkynes general mechanism (Figure 8). After precatalyst activation,
as an example (only a few possible routes are considered; other consequent oxidative addition, coordination, insertion, and
isomeric structures and different regioisomers at the alkyne insertion reductive elimination steps lead to the final product, which is
steps are omitted for clarity). released after dissociation. The same consideration for
precatalyst activation and regioselectivity on the insertion
reaction also requires precatalyst activation. This stage may step is applicable here, as discussed above for Z−H addition.
proceed to generate a low-valent metal complex (Figure 6B The mechanism is usually simpler and involves fewer possible
and C). However, this stage may be more diverse than cross- pathways since only the M−Z bond is available for insertion.
coupling since ligand substitution and the formation of thiolate In contrast, both M−Z and M−H bonds are available for
(and Se or Te analogues) complexes of the general formula insertion for the Z−H addition process (cf. Figures 6 and 8).
M(ZR′)n are also sufficient to initiate a catalytic cycle (Figure Noncatalytic side reactions may also take place and lead to
6D). All possible routes for the addition reactions are not poor stereoselectivity and the formation of Z- and E-isomers,
shown in Figure 6 for clarity, and particular reactions will be whereas the catalytic cycle is expected to give Z-isomers with
discussed in the sections below. high selectivity.
Alkyne insertion is the key stage required for all catalytic Comparing the considered catalytic reactions (Figures 5, 6,
cycles and all types of metals and oxidation states. As a and 8), one may notice that cross-coupling reactions typically
Chem. Rev. 2022, 122, 16110−16293
Figure 7. Possible routes of the metal-mediated Z−H bond addition reaction exemplified in the case of alkyne hydrotitration. Adapted with
permission from ref 140. Copyright 2020 American Chemical Society.
be achieved only in the case of selective transformation with

minimized (better, completely avoided) contribution from the
side reactions.
3.2. Nature of Catalytically Active Species
In the previous section, general mechanistic frameworks were
discussed with the metal center placed in square brackets [M].
Such notation is very often used in the reactions described in
the present review (or similar versions, such as MLn, etc.,
without specifying the exact number and type of ligands).
These notations mean that the exact arrangement of the
catalytically active center is omitted or, not uncommonly, not
known. This is one of the most intriguing questions in the
considered field of catalysis. Although the elementary steps
involved in catalysis are fairly well-known, the nature of
catalytic centers remains a puzzle.
The presence of a lone pair on the chalcogen atom (Z = S,
Se, Te) capable of easy coordination to the metal center brings
a new level of molecular complexity to the catalytic system.
Monometallic metal species are not the only metal-containing
component even in the presence of strong coordinating
Figure 8. Z−Z bond addition reaction to the alkyne and a general ligands, such as phosphine or NHC ligands. The coordination
catalytic cycle. of chalcogen atoms to another metal center gives rise to
bimetallic species and metal clusters. These structures were
involve metal centers in higher and lower oxidation states (i.e., observed experimentally, characterized in solution, and studied
Pd(II)/Pd(0) catalytic cycle, etc.) because activation of one of by X-ray analysis (see, for example, refs 141 and 142). Further
the reagents requires oxidative addition. In addition, product chain growth via the coordination network results in the
release in cross-coupling requires reductive elimination (Figure formation of coordination polymers [M(ZR)2]n, which are
5). Changes in the metal oxidation state also typically take insoluble in common organic solvents and bear a “nanosalt”
place in the case of the Z−Z bond addition reaction since, as structure.143 Monometallic complexes and clusters with the
above, Z−Z bond activation requires oxidative addition general [M(ZR)2]n formula may be easily accessed in reaction
(Figure 8). However, the Z−H bond addition reaction may mixtures (Figure 9) and were studied in details using
represent an exception, with two different possibilities available computational modeling at the DFT level (Figure 10).144
(Figure 6). In addition to a Pd(II)/Pd(0) catalytic framework, Amazingly, all of the components (monometallic complexes,
the whole catalytic cycle may proceed without changing the clusters, and nanoparticles) may possess catalytic activity and
oxidation state (i.e., Pd(II)-based catalytic cycle) because the lead to the formation of a final product. Depending on the
RZH reactant may react with the metal center via the ligand reaction conditions, either soluble metal species make the
substitution process, and product release may involve major contribution to product formation (i.e., homogeneous
protonolysis (Figure 6D). catalysis) or insoluble metal-containing particles are the active
Both catalytic methodologies, cross-coupling and addition form of the catalyst (i.e., heterogeneous or nanoscale catalysis).
reactions, require optimized high-performance catalysts to Determining the nature of catalytically active species is a
achieve large TON/TOF values, functional group tolerance, cutting-edge challenge and in many cases may still remain
and low catalyst loadings. In the case of addition reactions, unsolved.
optimization toward high selectivity is another important In some cases, the formation of cocktail-type catalysis144 can
target. High atom efficiency and improved green metrics may be expected with a number of pathways simultaneously
Chem. Rev. 2022, 122, 16110−16293
Figure 9. Formation of monometallic species M(ZR)2, metal clusters,

and coordination polymers [M(ZR)2]n. Adapted with permission Figure 11. Cocktail-type nature of the catalytic cycle with the
from ref 144. Copyright 2012 American Chemical Society. possibility of involving monometallic species (n = 0), clusters (n −
small value), or nanoparticles (n − large value). Adapted with
permission from ref 144. Copyright 2012 American Chemical Society.
contributing to product formation (Figure 11); i.e., metal 3.3. Difficulties in Catalyst Recycling
species with different numbers of metal atoms (different n The complicated nature of catalytic systems imposes significant
values in Figure 11) are simultaneously accessible in the difficulties in catalyst recycling. The catalyst is difficult to
catalytic system, and the corresponding catalytic cycles operate isolate after the reaction, or loss of catalytic activity is observed
after completion of the reaction and separation.
in parallel. The phenomenon of leaching was observed in the There are well-established procedures for the recycling of
case of [M(ZR)2]n nanoparticles, and adaptive tuning was also heterogeneous catalysts. However, in the case of leaching and
reported.144 metal transfer to the solution, complete catalyst recovery is not
Figure 10. Molecular structures of acyclic (top: n = 1, 3, 6, and 8) and cyclic (bottom: n = 3−6) [M(ZR)2]n complexes exemplified for palladium
thiolates. Adapted with permission from ref 144. Copyright 2012 American Chemical Society.
Chem. Rev. 2022, 122, 16110−16293
possible. Moreover, most active components (most easily nonactivated aryl chlorides, Triphos [Me-C(CH2PPh2)3]
leached locations at the nanoparticles) are rapidly washed out, demonstrated good results.150
and the catalyst loses activity over the reuse cycles. Palladium carbene complexes have played an important role
Recycling in the case of homogeneous catalysis is difficult, in the development of the area, and they demonstrated good
but the system becomes even more difficult if insoluble results in cross-coupling reactions with the formation of C−C
nanoparticle precipitates form during the reaction. Indeed, no bonds, as well as C−N and C−O bonds.151,152
general procedures have been developed until now for catalyst The application of Pd carbene complexes in thiolation
recycling and reuse if interplay between homogeneous and reactions has led to high-yield synthesis of sulfenylation
heterogeneous catalysis is observed in the same reaction vessel. products.153 However, the especially “beautiful link between
Cocktail-type behavior significantly complicates catalyst Pd and heterocycle carbenes” (Nolan152) was revealed after
recovery. This issue remains a paramount challenge for many carbenes synthesized in Nolan’s154,155 and Organ’s156−160
reactions in the discussed field. groups were introduced into synthetic practice.
Nolan’s complexes�a novel class of NHC ligands and bulky
4. CATALYTIC CROSS-COUPLING REACTIONS (Z = S, and electron-rich IPr*OMe151,152,154,155�demonstrated high
Se, Te) activity in the reaction of aryl halogenides with aromatic and
aliphatic thiols and allowed the reactions between aryl
4.1. Palladium-Catalyzed Transformations
halogenides and thiols to be carried out with high yields
4.1.1. Cross-Coupling with Thiols. As noted earlier, the (Scheme 3).
usage of Pd(0) in the cross-coupling reaction for the formation A large family of NHC ligands and their complexes with Pd
of the carbon−heteroatom bond, in addition to the carbon− proposed by Organ ([Pd-PEPPSI-IPent(L)], where L = 3-
carbon bond, has significantly changed the synthetic organic chloropyridine, picoline, morpholine, etc.) demonstrated
chemistry. Splendid techniques for obtaining the C−N and C− exceptionally high efficiency in various cross-coupling reac-
O bonds and, to a lesser degree, the C−S bond (because of the tions,156−160 including sulfination. Suffice it to say that those
formation of metal complexes with sulfur-containing com- complexes allow conducting the sulfination of inactivated
pounds that changes the catalytic activity of the former and (sterically and electronically) aryl chlorides at temperatures
because of the unpleasant smell of thiols) have been proposed. close to room temperature. At that point, the proposed series
However, the demands in the synthesis of various sulfur- of complexes allows choosing the most efficient catalyst for a
containing compounds have triggered the development of particular reaction (Figure 12, Scheme 4).
various methods, in which thiols are replaced with other Lee and co-workers161 used a system of Pd salts of N-amido
sources of sulfur (with low toxicity and without an unpleasant imidazolium as catalyst precursors. Their results demonstrated
smell).58 the importance of the nature of the base. Thus, ArBr and ArI
It should be remembered that for a long time cross-coupling required different ligands and bases to reach maximal product
reactions, including C−S bond formation, have been based on yields (Scheme 5).
the use of Pd complexes as catalysts. For the first time, this Aryl iodides and bromides were mechanochemically
reaction was carried out by the Japanese chemists Kosugi and thiolated under the action of aromatic and aliphatic thiols
Migita, who originally used R3SnSR′ thiol derivatives. Later, under catalysis by the Pd−PEPPSI−IPent carbene complex
Kosugi and Migita carried out the reaction with the thiol itself using sand as a grinding agent and tBuOK as a base. The
(Scheme 2, A).145,146 Similar studies were performed by reaction of PhI with PhSH proceeded quickly with 92%
Murahashi and co-workers by using vinyl bromides and lithium yield162 (Scheme 6).
or sodium salts (Scheme 2, B).147 The addition of zinc prevents the formation of disulfides.
According to the authors’ results, the ball-milling process has
Scheme 2 advantages over reactions in solution.
An efficient Pd/PTABS catalytic system (where PTABS is a
triazaphosphaadamantane derivative) allows the reactions of
aryl and heteroaryl chlorides with aromatic and aliphatic thiols
with excellent yields at a low temperature (50 °C) (Scheme
7).163
The reaction of chloropyrimidines, as well as chlorine
derivatives of purines and ribonucleosides with RSH (R = Ar,
Alk), proceeded with good yields up to 88% (Scheme 8).
Verma and co-workers proposed a new ligand.164 They
obtained a novel series of ligands with a triazole ring, of which
(1-pyridine-2-yl)-1H-benzo[d][1,2,3]triazole was the most
efficient. Upon using this ligand, the Pd(OAc)2-catalyzed
The subsequent development of thiol cross-coupling has reaction of aryl(heteroaryl)bromides with substituted thio-
been related to the application of bidentate ligands that allow a phenols and octylthiol proceeded with high yields in the case
decrease in the palladium concentration and an increase in the of ArSH and with good yields in the case of OctSH (67%)
product yield. It also allows the use of aryl bromides, (Scheme 9).
aryltrifluoromethanesulfonates, and activated aryl chlorides, The known idea proposed by Li165,166 implies the use of a
in addition to aryl iodides. mixture of ligands for the detection of the most efficient ligand,
A significant role in this process was played by Hartwig and and it has been recently employed by Buchwald for the
Buchwald, who proposed various ligands (L = Dippf, synthesis of amines167 and by Peng and co-workers168 for the
Xantphos, DPEphos, CyPF-tBu, etc.).148,149 In the case of synthesis of heteroarylthiols. A mixture of Xantphos and CyPF-
Chem. Rev. 2022, 122, 16110−16293
Scheme 3
The reaction with α-naphthylthiol and ortho-anisylthiol did

not proceed. Thiols with electron-withdrawing groups
provided lower yields.
Pd-catalyzed thiolation of unprotected bromine indazoles
with aromatic and aliphatic thiols was carried out. At that time,
the opening of the nitrogen-containing ring was avoided,
possibly due to the use of the third generation Josiphos SL-
J009-1 Pd G3 Buchwald Pd catalyst (Scheme 12).170
Figure 12. Pd−PEPPSI complexes. Alami and co-workers realized classical Pd catalysis,
according to Buchwald−Hartwig, in the reaction of aryl-
tBu at a ratio of 3:1 with Pd2(dba)3 efficiently catalyzed the (heteryl)halogenides (X = I, Br) with thioglucosides (Scheme
reaction of Het(Ar)X with aromatic and aliphatic thiols 13).171
(Scheme 10). In a screening of various bidentate and monodentate ligands,
Each ligand supposedly performs its own function, but Pd(OAc)2-Xantphos-Et3N demonstrated the best results.
CyPF-tBu plays the main role. Under these conditions, 22 hetero(aryl)halogenides were
Hierso, Saeys, and co-workers used a novel binuclear catalyst introduced into the reaction with β-thioglucose, and the yields
(A) in the S-cross-coupling of thiophenol with 2-chloroheter- were in the range of 72−99%, with the exception of
oarenes. The authors synthesized a series of eight phosphor- (2R,3R,4S,5R,6S)-2-(acetoxymethyl)-6-[(4-nitrophenyl)thio]-
substituted ferrocenyl ligands, of which L = 1,1′,3,3′-tetrakis- tetrahydro-2H-pyran-3,4,5-triyl triacetate (61%).
(diphenylphosphino)ferrocene demonstrated the highest Reactions with other sugars containing the thio group
activity (Scheme 11).169 proceeded in a similar manner. 4-Methyl-7-thioumbelliferyl-β-
Scheme 4
Chem. Rev. 2022, 122, 16110−16293
Scheme 5
Scheme 6 The recyclable palladium−prolinate complex Pd(L-Pro)2 was

proposed for the cross-coupling reaction between aryl iodide
and various thiols (Scheme 17, A).83 In the case of p- and o-
iodonitrobenzene and thiols with donor substituents, very high
yields (up to 100%) were obtained. The catalyst was recycled 5
times (93−85%), but the yield dropped significantly (20−
50%) upon moving to the reactions of 2-iodobenzoic acid with
D-cellobioside (MUS-CB) was synthesized according to the thiols with electron-donating groups. The stages of oxidative
proposed method (Scheme 14).
coupling and reductive elimination (Pd(II) ↔ Pd(0)) are
In continuation of the works on arylation of thiosugars, 1-
proposed to proceed with the opening and subsequent
aminobiphenyl was introduced by using the corresponding
reforming of a palladacycle.
cyclopalladate172 in water at room temperature (Scheme 15,
A).173 The use of the Pd(I) dimer as a catalyst in S-cross-coupling
The authors used the same complex as a catalyst for the allows selective substitution only at the C−Br bond in arenes
synthesis of S-linked saccharides and S-linked glycoconju- with Br, Cl, and OTf substituents (Scheme 17, B).178 In the
gates.174 This group also studied a tandem three-component S- case of aryl iodides and bromides, the reaction with AlkSNa
cross-coupling reaction and the Suzuki reaction producing and PhSNa proceeds with excellent yields (up to 99%).
unsymmetrical biaryl thioglycosides (Scheme 15, B).175 A complex of Pd(II) with a Schiff base catalyzes the
Cross-coupling with C−S bond formation was used in a Pd- synthesis of pyrido[3′,2′:6,7][1,4]thiazepino[2,3-h][1,6]-
catalyzed reaction for the synthesis of 5-mercapto-function- naphthyridine derivatives upon UV−visible irradiation. The
alized pyrimidine nucleosides and their analogues (Scheme 15, process includes the stages of C(sp2)−S formation through C−
C).176 H activation (Scheme 18).179
The natural amino acid cysteine and a water-soluble Alper and co-workers180 carried out a Pd-catalyzed reaction
palladium complex were used to build aryl linkers in peptides of intramolecular thiolation with simultaneous carbonylation
and proteins (Scheme 16).177 (Scheme 19, A). As an example of thiophene synthesis, a
Scheme 7
Chem. Rev. 2022, 122, 16110−16293
Scheme 8
Scheme 9
domino process including Pd-catalyzed thiolation of brome- produces thiophenes in high yields, and variations in the
nyne with subsequent cyclization can be mentioned. It original structure allow varying the nature of substituents in
Chem. Rev. 2022, 122, 16110−16293
Scheme 10
Scheme 11
thiophene (Scheme 19, B).181 Another variant of such a sulfide and hydrosulfide, carbon disulfide, Bunte salts,
tandem one-pot reaction was realized by Wang and co-workers dithiooxamide, and sulfonyl hydrazide.
in the presence of phenyltrimethoxysilane. This results in the First, such sources of sulfur include salts of thiols. Buchwald
and co-workers183 used AgSCF3 to carry out a Pd cross-
formation of 2-phenylbenzothiophenes (Scheme 19, C).182
coupling reaction with aryl bromides to produce a variety of
4.1.2. Sulfur Sources Other than Thiols. Currently,
aryl trifluoromethyl sulfides (Scheme 20, A).
sulfur surrogates are widely used instead of thiols: thiourea, The use of a salt instead of gaseous HSCF3 made it possible
potassium thioacetate, potassium ethyl xanthogenate, thio- to obtain biologically active compounds, including an
cyanate precursors, thioacetamide, aminothiourea, sodium intermediate for the synthesis of Toltrazuril, under mild
Chem. Rev. 2022, 122, 16110−16293
Scheme 12
Scheme 13
Scheme 14
conditions with a high yield (Scheme 20, B).184 A similar and bromides and with moderate yields in the case of
introduction of the selenium analogue was carried out using chlorobenzene. During six cycles, the product yield remained
ammonium salt and nickel catalysis (Scheme 20, C).185 Lee practically unchanged (Scheme 21, A).189 Arylselenoacetates
and co-workers used indium salts to introduce a thiol group
were obtained by using the palladium complex Pd(OAc)2/
(Scheme 20, D).186−188
Cai and Zhao and co-workers showed that the Pd-catalyzed RuPhos as a catalyst in the reaction of aryl bromides with
reaction of Bu3SnSePh with ArX in an ionic liquid at 80−110 tricyclohexylsilylselenol under mild conditions (Scheme 21,
°C produced a product with high yields in the case of iodides B).190
Chem. Rev. 2022, 122, 16110−16293
Scheme 15
Scheme 16
Scheme 17
A hydrogen sulfide surrogate (HSTIPS) was used in a one- cyclization (with and without the addition of an electrophile)
(Scheme 22, A).181
pot synthesis of substituted thiophenes and benzothiophenes
Using sodium sulfide, Pd-catalyzed synthesis of (Z)-3-
via a two-stage, one-pot, cross-coupling reaction followed by arylthioacrylic acids and thiochromenones was carried out
Chem. Rev. 2022, 122, 16110−16293
Scheme 18
Scheme 19
(Scheme 22, B).191 By obtaining thiochromenones via a Another variant of such cyclization with the participation of
palladium-catalyzed four-component reaction, Wu and co- o-iodothiobenzanilide was also carried out using a “ligand-free”
workers showed the advantages of carrying out the reaction heterogeneous Pd/C catalyst. 2-Substituted benzothiazoles,
upon reagent encapsulation, and it allows avoidance of catalyst where R = Ar and Alk, were produced in high yields at room
poisoning and the formation of byproducts. A large family of temperature (Scheme 23, B).196
thiochromenones were synthesized by using this method Dong and co-workers synthesized 2-aminobenzothiazole
(Scheme 22, C).192 from 2-chloroanilines and dithiocarbamates in good to high
Starting from 2,3-dihalopyridines and Na2S in reactions yields by using N- and S-cross-coupling upon Pd(PPh3)4
involving cross-coupling and cyclization, 2-(hetero)arylthieno- catalysis (Scheme 23, C).197
[2,3-b] or [3,2-b]pyridines were obtained in good to high By many examples, Batra and co-workers demonstrated that
yields (Scheme 22, D).193
a Pd-catalyzed reaction of 2-bromophenylthiourea with
An interesting Pd(II)-catalyzed trimolecular reaction involv-
isocyanide produced 4-substituted imino-4H-benzo[d][1,3]-
ing coupling and annulation reactions occurs between 2-
(alkynyl)quinoline-3-carbaldehydes and Na2S in the presence thiazin-2-amines (Scheme 23, D).198
of benzyl chloride, producing 2,3-substituted cyclopenta[b]- Intermolecular coupling with the participation of thiourea
quinolin-1-ones containing an RS group (18 examples, yields followed by cyclization and the production of 2-substituted
up to 88%).194 benzothiophenes were carried out using a Pd(0)/Triphos
Thiourea is widely used in intra- and intermolecular catalytic system (Scheme 24, A).150 This is an example of
reactions as a source of sulfur. As an example, the preparation obtaining thieno[3,2-b]thiophenes (Scheme 24, B). The
of aminobenzothiozoles via a reaction involving cross-coupling reaction of thiourea with aryl halides under these conditions
or C−H activation with “ligand-free” palladium can be proceeds as a domino reaction, resulting in symmetric diaryl
mentioned (Scheme 23, A).195 sulfides in 24−98% yields.150
Chem. Rev. 2022, 122, 16110−16293
Scheme 20
Cai and co-workers developed an efficient synthesis of (20 examples, yield up to 98%) lead to the production of 9-
isothiochromene derivatives using a Pd-catalyzed reaction of 2- sulfenyl phenanthrenes as a result of electrophilic annula-
(phenylethynyl) benzyl bromide with thiourea, which included tion.200 In a three-component reaction under micellar catalysis
thiolation and hydrothiolation steps (14 examples with yields conditions in water, a one-pot synthesis of unsymmetrical
up to 99%) (Scheme 24, C).199 Pd-catalyzed and iodine- arylalkylthioethers was carried out (Scheme 24, D).201 The use
promoted reactions of 2-(1-alkynyl) biphenyl with disulfides of 2-benzyl-1,3-dithianes as a source of sulfur allows aryl and
Chem. Rev. 2022, 122, 16110−16293
Scheme 21 In a reaction of aryl halides with potassium thiocyanate, an

ionic palladium complex was used as a catalyst precursor
(Scheme 26).209
Phenylthioacetate was used as a source of sulfur in the
reaction with aryl bromides, and asymmetric sulfides were
obtained in high yields (Scheme 27, A).210 The same result can
be obtained in a three-component reaction using potassium
thioacetate salt (Scheme 27, B).210
In their work, Jiang and co-workers provided biologically
active molecules containing aryl methyl sulfide, sulfoxide, and
sulfonyl groups and proposed a new method for introducing
the “MeS” group in a Pd-catalyzed three-component reaction
vinyl thioether fragments to be obtained in a single molecule of aryl(heteroaryl) chloride, potassium thioacetate, and
via a Pd-catalyzed reaction (Scheme 24, E).202 dimethyl carbonate (Scheme 27, C).96
Sodium thiosulfate is a cheap and nontoxic source of The method was applied to the thiomethylation of
sulfur,203 and it can be used for the production of thiophenols nucleosides (7 examples) and the production of pesticides
(Scheme 25, A).204 (10 examples, including Terbutryn, Irgarol, and Simetryn in
The synthesis of 1,4-benzothiazines that included double gram quantities) and pharmaceuticals (Na2S2O3 was used
C−S bond formation was carried out (Scheme 25, B).205 An instead of KSAc) (Scheme 27, D).
efficient route for the preparation of 2-aminobenzothiophenes Aryl(heteroaryl) chlorides react in a Pd/XPhos catalytic
by using Na2S2O3 was proposed by Yang and co-workers system when using KOtBu as a base (Scheme 28, A).211 The
(Scheme 25, C).206 Using Pd(II)−NHC as a catalyst and the reaction did not proceed with aliphatic sulfur derivatives.
ionic liquid [Cpmim]Cl, which showed the best results when Potassium thioacetate as an HS-group surrogate was used in
optimizing the reaction conditions, various 4-sulfenylisoxazole an interesting reaction of Pd-catalyzed C−S cross-coupling
derivatives were obtained in a three-component reaction of followed by endo−dig cyclization to obtain dithienopyridines
acetylinic oximes with Na2S2O3 and aryl halide. The reaction and dithienopyrazines and compounds with important photo-
includes oxypalladation at the triple bond and the reaction of physical and electrochemical properties (Scheme 28, B).212
the palladium intermediate with RSSO2ONa proceeding with Here are examples of the synthesized 2,6-disubstituted
the elimination of SO3.207 Unsymmetrical arylalkylthioethers dithienoacenes.
were synthesized in a three-component Pd-catalyzed reaction In the reaction with aryl bromides catalyzed by the Pd/
by using Na2S2O3 and RX (Scheme 25, D).208 XPhos complex, benzylthioacetate produces arylbenzyl sulfides
Scheme 22
Chem. Rev. 2022, 122, 16110−16293
Scheme 23
in good to high yields. The same result can be obtained by A large series of alkylaryl sulfides (20 examples) were
using benzyl bromides with potassium thioacetate (Scheme 28, obtained in 56−88% yields via the Pd(TFA)2/Xantphos-
C).213 catalyzed reaction of aryl triflates with methyl (3-alkylthio)-
Potassium thioacetate was used as a surrogate for obtaining propanoate as a source of the AlkS group.226 2,2-Diphenyl-1,3-
S-aryl thioacetates (Scheme 28, D).214 oxathiolane was used as a vinyl sulfide surrogate for the
A combination of palladium/norbornene and copper allows preparation of arylvinyl sulfides (Scheme 31).227
us to obtain 2-(arylthio)aryl ketones in the reaction of aryl Vinyl sulfide is generated under basic conditions. A large
iodides with thioethers. Upon cooperative catalysis, the series of compounds were obtained in good to high yields.
C(O)−S bond is cleaved with simultaneous C−H acylation Thus, when using bromobenzene, the product yield was 95%
and ipso-thiolation in the reaction (Scheme 29, A).215 A similar (isolated yield 85%). The exception was p-CF3C6H4Br, which
reaction proceeds upon Pd-catalyzed interaction of aryl iodides did not react. An unusual sulfur source is used for the
with selenium ethers (Scheme 29, B).216
production of unsymmetrical diaryl sulfides (Scheme 32).228
Arylthioesters, readily obtained from the corresponding
A cyclopalladate with the same ligand was a precatalyst in
carboxylic acids, can themselves serve as starting materials for
the reaction for the preparation of diaryl sulfoxides with the
the preparation of thioethers in metal-catalyzed decarbon-
ylation. This reaction is catalyzed not only by palladium but participation of arylbenzyl sulfoxides and aryl chlorides
also by nickel and rhodium.217−223 Lee and co-workers (Scheme 33, A).229 A Pd-catalyzed arylation of sulfenate salts
managed to overcome the issues of this reaction involving 2- obtained from sulfenic acids, which, in turn, were formed via
pyridyl thioesters in 2020 only (Scheme 30, A).224 The pyrolysis of tert-butyl sulfoxides, was carried out (Scheme 33,
proposed reaction mechanism (Figure 13) included catalyst B).230
activation via reduction of the Pd(II) catalyst precursor and Double arylation in tBu2S(O) is possible, and diphenyl
the catalytic cycle with the sequence of reagent coordination, sulfoxide is formed in 91% yield. The phenyl sulfoxide group
oxidative addition, decarbonylation, and reductive elimination. can be transferred by methyl phenyl sulfoxide. Its arylation by
The preparation of various sulfides via intramolecular aryl bromides upon Pd catalysis allows phenylaryl sulfoxides to
decarbonylation of thioethers catalyzed by a palladium be obtained (Scheme 33, C).231 A complex of Pd with
complex was carried out without a base at high temperature bidentate carbene was obtained from a bis(imidazolium) salt
with excellent product yield (Scheme 30, B).225 (L).
Chem. Rev. 2022, 122, 16110−16293
Scheme 24
Introduction of the CF3SO2 group resulting in the formation Cooperative Pd/Cu catalysis without a ligand is used in a
of aryl(heteryl)triflons occurs in the reaction of ArOTf with one-pot synthesis of arylsulfonamides in the reaction of aryl
Na-triflinate (Scheme 34).232 In the case of aryl chlorides, the iodides, DABSO, and O-benzoyl hydroxylamines (Scheme 36,
reaction proceeds with lower yields and under more severe A).241 This reaction successfully proceeds when replacing aryl
conditions. iodide with arylboronic acid (Scheme 36, B).242 It should be
In 2010, Willis and co-workers obtained aryl N-amino- noted that the preparation of such an important class of
sulfonamides via Pd-catalyzed synthesis by using DABSO for sulfonamides, which includes known drugs, can be carried out
the first time233 (see refs 103 and 234). Likewise, palladium-
via an electrophilic amination of sodium sulfinates catalyzed by
catalyzed conversion of aryl iodides to sulfonyl fluorides
proceeds upon using DABSO as the SO2 source and CuBr2 (Scheme 36, C).108
Selectfluor as the source of fluorine (Scheme 35, A).235 The oxidative Pd-catalyzed three-component reaction of
Pd-catalyzed three-component reactions with the partic- arylboronic acid with SO2 and hydrazine gave aryl N-
ipation of hydrazines proceeded very well (Scheme 35, aminosulfonamides in good to excellent yields (Scheme 36,
B).236,237 Upon interaction with alkyl halides and other D).236 A reaction mechanism involving SO2 insertion into the
electrophiles, the aminosulfonation product forms unsym- Pd−Ar bond was proposed (Figure 14). This method was
metrical sulfones with different functional groups (Scheme 35, employed to obtain a methyl ester of the Casodex derivative
C).238−240 (Scheme 36, E).243 Aminosulfonation proceeds via a radical
Chem. Rev. 2022, 122, 16110−16293
Scheme 25 Scheme 27
Scheme 26
The same group carried out a similar reaction with

aryl(heteroaryl)boronic acids in the presence of aryl, benzyl,
styryl, and alkyl halides (Scheme 38, B).249
Arylsulfonyl quinones with pharmaceutical potential were
obtained via the Pd-catalyzed reaction of quinone and
mechanism in the reaction of aryldiazonium salt with DABSO benzoquinone with arylsulfonyl chloride with neutral and
and hydrazine (Scheme 36, F).244,245 electron-donor substituents (15 successful examples, yields up
The reaction of aryl iodides with inorganic sulfites and to 89%).250
hydrazines under Pd catalysis allows aryl-N-aminosulfonamides Yoshida and co-workers carried out Pd-catalyzed synthesis
to be obtained (Scheme 37, A). 246 Thus, potassium of various sulfoxides via the action of sulfinate esters on aryl-
metabisulfite can replace SO2 in the Pd-catalyzed amino- and alkenylboronic acids (Scheme 39).251 The method allows
sulfonylation reaction. When using aryl bromides, the product one to obtain sulfoxides with various functional groups.
yield decreases significantly. 4.1.3. Heterogeneous Palladium-Catalyzed S-Cross-
In three-component reactions of aryl halide and K2S2O5 Coupling. In general, heterogeneous Pd catalysts in the S-
under Pd catalysis, sulfones or sulfamides are formed cross-coupling reaction have been understudied.
depending on the nature of the third component (Scheme A heterogeneous palladium complex formed by PdNPs on
37, B).247 the TATAM polymer produced via the condensation of
Ramón et al. studied the reaction of arylboronic acids with 4,4′,4″-(1,3,5-triazine-2,4,6-tribenzaldehyde) and melamine
sodium metabisulfite as a source of SO2 in an unusual reaction catalyzes the reaction of bromobenzene with selenium powder
medium (deep eutectic solvents) with PdCl2 as a catalyst. (K3PO4, DMSO, 100 °C), with the formation of diphenylse-
Under the reaction conditions, the resulting sodium sulfinate lenide containing a diphenyl impurity (84% and 15%,
can be intercepted by an electrophile, nucleophile, or radical. respectively). Symmetric diaryl(3-pyridyl)selenides with elec-
In the last two cases, sulfides are formed (Scheme 38, A).248 Of tron-withdrawing and electron-donating substituents were
note, an iron salt can be used instead of Pd. The reaction obtained in good yields (62−84%). The catalyst was recycled
medium, together with the catalyst, was used three times, and in four cycles (84%, 83%, 80%, and 72%) (Scheme 40).252
the activity was fully preserved. It is assumed that the activity is Peptide nanofiber-decorated PdNPs (PdNPs-PNF) proved
determined by the small size of the formed PdNPs, and at that to be an effective catalyst in the reaction of aryl halides with
time, the morphology of the particles has no impact on the thiourea and 2-mercaptobenzothiazole. In both cases, sym-
activity. metric diaryl sulfides were formed (Scheme 41, A).253 Upon
Chem. Rev. 2022, 122, 16110−16293
Scheme 28 Scheme 30
Scheme 29
Figure 13. Decarbonylative C(sp2)−S bond formation catalyzed by

Pd.
Scheme 31
recyclization, the yield decreases from 95% to 81% in four

cycles.
A palladium complex on an amphiphilic support consisting
of a polystyrene−polyethylene glycol copolymer in water
demonstrated good results in the preparation of unsymmetrical
diaryl sulfides (Scheme 41, B).254
Heterogeneous Pd(II)−silica-covered magnetic NPs proved
to be an efficient catalyst for cross-coupling reactions,
including the formation of the C(sp2)−S bond (Scheme 41, accompanied by a significant decrease in the product yield
C).255 The catalyst can be recycled. (99% → 60%) (Scheme 41, D).256
A reaction of aryl halides with benzylthiol and thiophenol Das and co-workers showed257 that PdNPs on a solid
proceeds with excellent yields when using palladium catalysis support catalyzed a thiolation reaction of nitro-substituted aryl
on silica diphenylphosphinite. However, recycling (5 cycles) is halides (including chlorides) in the absence of ligands
Chem. Rev. 2022, 122, 16110−16293
Scheme 32 Scheme 35
Scheme 33
Scheme 36
Scheme 34
(Scheme 41, E). The nitro group can be reduced by silane to

produce amino derivatives.
Of note, earlier unsymmetrical thioesters with a p-amino-
phenyl group were obtained in a reaction catalyzed by “ligand-
free” palladium in water under microwave irradiation (Scheme
41, F).258
4.1.4. Pd(II)-Catalyzed Oxidative Reactions. In the the conditions (Scheme 42, A).259 In the case of an alkyl
classical variant of cross-coupling with ArHal, catalysis is derivative, alkyl phenyl sulfide was formed (Scheme 42, B).
carried out by Pd(0) complexes, and changing the leaving The oxidative decarboxylation reaction is also catalyzed by
group to CO2H, NHNH2, etc. renders the oxidative cross- Pd(II) in the presence of silver or copper salts as oxidizing
coupling, which is catalyzed by Pd(II). Such reactions include agents (Scheme 43, A).260 Cai and co-workers described
the Chan−Lam-type reaction, where phenyltriethoxysilane is methylthiolation upon decarboxylation of ortho-nitrobenzoic
used as an organoelement compound. Pd catalysis was carried acids with DMSO (Scheme 43, B).261
out in the presence of CuF2, and ArS2O3Na was used as a Diaryldisulfides or diselenides can be used as sulfenylating or
sulfur source. Thioether or thioester was formed, depending on selenating agents, respectively. Thus, upon interaction of 2,6-
Chem. Rev. 2022, 122, 16110−16293
Scheme 39
Figure 14. Oxidative formation of N-aminosulfonamides via a Chan−

Lam-type reaction.
Scheme 37
Scheme 40
mechanism reflects the general processes for the oxidative

reactions being considered (Figure 15). In addition to ease of
Scheme 38 use, similar to decarboxylation, the proposed method produces
no waste.
Of note, as early as 2012, Ranu and co-workers carried out a
reaction of ArN2BF4 with various dichalcogenides by using Zn
powder and MW radiation. The reaction resembles the
Sandmeyer reaction, and it is assumed that (PhY)2Zn plays
the role of the nucleophilic reagent (Scheme 44, B).265 N-
Tosylhydrazones in a Pd-catalyzed reaction with alkenyl
thioether allowed us to obtain alkenyl thioethers with good
yields and stereoselectivity (Scheme 44, C).266
4.1.5. C−H Functionalization. C−H activation catalyzed
by transition metal complexes is a relatively young field that
has received exceptional attention and development and
naturally affects the Pd-catalyzed formation of the C−S
bond.26,45,58,267
The direct introduction of a functional group into an
aromatic system is a great achievement of modern organic
chemistry. It is a powerful tool for producing sulfur-containing
dialkoxybenzoic acid with a palladium salt in the presence of agents for pharmaceutical and medicinal chemistry268 and
oxidizing agents, the proceeding reaction with diaryl disulfides organic electronics.269,270
or diselenides produces diaryl sulfides or selenides (Scheme 43, A special group of reactions is represented by reactions
C).262 including C(sp2)−H functionalization with the formation of a
Zhang and co-workers263 used Pd(II)-catalyzed decarbox- C(sp2)−S bond (various thioethers) with the participation of
ylative C−S cross-coupling to thiolate quinolone derivatives SO2-containing reagents: sulfonyl chlorides, sulfonyl hydra-
(Scheme 43, D). In the case of R1�R2�R3�R4�H and zides, and sodium sulfinate (RSO2Cl, RSO2NHNH2, and
R3�R4�Me, the reaction does not proceed. RSO2Na).271
Oxidative coupling can proceed with arylhydrazines Beller and co-workers used electron-rich arenes in a Pd-
(Scheme 44, A).264 In the presence of p-NO2 substituents in catalyzed reaction with ArSO2CN to produce diaryl sulfides
both reagents, the reaction does not proceed. A proposed (Scheme 45, A).272 Upon catalysis by Pd(OAc)2 in trifluoro-
Chem. Rev. 2022, 122, 16110−16293
Scheme 41 Scheme 43
Scheme 44
Scheme 42
Figure 15. Catalyzed by Pd(II) oxidative coupling with arylhy-

acetic acid, mesitylene reacts with p-TolylSO2CN, producing drazines.
unsymmetrical diaryl sulfide in high yields; however, when
using PhSO2CN, the yield drops sharply (38%). The reaction
of arylsulfonyl hydrazides catalyzed by Pd(II) (in the presence
of an oxidizing agent) occurs with the C(sp3)−H bond as dioxane produce good isolated yields (Scheme 45, C).274 In
(Scheme 45, B).273 the case of linear aliphatic esters, the yields decreased (34−
An interesting example is the direct thiolation of ethers 65%). The addition of TEMPO stops the reaction, which is in
(C(sp3)−H bonds) by sodium sulfinate, catalyzed by accordance with the radical mechanism.
palladium in the presence of an oxidizing agent, which is a Direct Pd-catalyzed aryl(alkyl)thiolation of arenes contain-
convenient way to obtain arylalkyl sulfides. Cyclic ethers such ing donor substituents was carried out with N-thiosuccinimide,
Chem. Rev. 2022, 122, 16110−16293
Scheme 45
which proved to be the best sulfenylating agent under the

proposed conditions (Pd(OAc)2, TFA) (Scheme 46, A).85
Figure 16. Sulfenylation of the C(sp2)−H bond via Pd(IV)
Scheme 46
formation.
Scheme 47
Scheme 48
In the presence of ortho-Br in the sulfenylating reagent,

dibenzothiophene and benzo[a]phenoxathiine derivatives are
formed in two-stage reactions. The yield after the two stages is with a good yield, whereas furan and pyrrole do not react. In
shown (Scheme 46, B). The authors considered the reaction the case of 2-phenylbenzofuran, the yield was 46%. The
mechanism with the participation of Pd(IV) (Figure 16). catalytic reaction cycle is shown in Figure 17.
An example of the reaction with the directing group is a Formation of 3-sulfenylbenzofuran or 3-sulfenylindole can
reaction carried out independently by two groups under occur in various ways, including metal-catalyzed annulation of
different conditions (Scheme 47).275,276 2-alkynylphenols or 2-alkynylanilines followed by reaction with
An excellent combination of the Chan−Lam reaction and a disulfide.278,279
oxidative sulfenylation of the C−H bond was accomplished by The same authors showed that a combined catalytic action
Jiang and Wu and co-workers to introduce an ArS group into of Pd and Cu on 2-alkynylphenols and 2-alkynylamines in the
indole and electron-rich arenes by using cooperative Pd/Cu presence of ArB(OH)2 and S8 leads to the production of 3-
catalysis, arylboronic acids, and elemental sulfur (Scheme sulfenylbenzofurans and 3-sulfenylindoles in good to high
48).277 yields (Scheme 49, A).280
Under the optimized conditions (Pd(OAc)2 (5 mol %) − Double sulfenylation upon using sulfur powder in the
CuI (1 equiv) − Phen (1.1 equiv) − Cs2CO3, Ag2CO3 (2 reaction of indoles with cyclohexanones results in benzothieno-
equiv), [bmim]Cl, 80 °C, 6 h), the yields for N-substituted [2,3-b]indoles via dehydrative−dehydrogenative stages. This is
indoles reach 65−90%. The unsubstituted indole itself a new one-step route to the important class of biologically
produces sulfide in the reaction with PhB(OH)2 in 81% active compounds (Scheme 49, B).281 The authors propose the
yield. Imidazo[1,2-a]pyridine reacts under these conditions following possible mechanism for this reaction (Figure 18).
Chem. Rev. 2022, 122, 16110−16293
Figure 17. Pd/Cu catalysis in C(sp2)−H sulfenylation by ArB(OH)2/

S8.
Scheme 49
Figure 18. Pd(II)-catalyzed reaction of indole with cyclohexanones

and S8.
Scheme 50
In continuation of their work on the preparation of In 2018, two groups independently proposed simple and
benzothiazoles via a Pd-catalyzed intramolecular reaction of convenient palladium-catalyzed intramolecular thiolation re-
thiobenzanilide, Inamoto, Kondo, and Nozawa carried out the actions involving C−H activation. Xu, Tan, and co-workers
reaction in water (Scheme 50, A).282 Under mild conditions, carried out the reaction (C−H/S−H coupling) of 2-
the reaction proceeds with a good yield, in some cases, with a biphenylthiols in a PdCl2/DMSO system. DMSO acts not
quantitative yield. A similar intramolecular formation of only as a solvent but also as an oxidizing agent (Scheme 51,
C(sp2)−S bonds allowed Liu and co-workers to obtain A).111 The method was used for synthesizing helical
glucosyl thiourea substrate sugar-functionalized benzothiazoles dinaphthothiophene and DBTDT (semiconductor) (Scheme
(Scheme 50, B).283 Dong and co-workers prepared 2- 51, B).
aminobenzothiazoles via a Pd-catalyzed intramolecular reac- Sakai and co-workers also synthesized dibenzothiophenes
tion involving C−H activation promoted by phenyl iodide from 2-biphenyl disulfides using the PdCl2/DMSO system
(Scheme 50, C).284 (C−H/S−H coupling) (Scheme 52, A).286 In the case of
Wirth and Xu demonstrated the possibilities of electro- compounds with substituents in sulfur-bonded aromatic rings,
chemical synthesis of benzothiazoles and thiazolopyridines in a the reactions proceeded with lower yields (61−89%).
continuous flow that did not require a catalyst (Scheme 50, Dibenzoselenophen was obtained with an almost quantitative
D).285 As already mentioned, the dibenzothiophene moiety is yield in 24 h under the same conditions (Scheme 52, B).
of great importance in both pharmaceutical areas and organic To confirm the mechanism, the reaction of 2-phenyl-
electronics. benzothiol was carried out. Dibenzothiophene was obtained
Chem. Rev. 2022, 122, 16110−16293
Scheme 51 Scheme 53
In the presence of salts (NiCl2, LiCl), other products are

obtained as mixtures with the predominant formation of one of
them. The molecular structures of these compounds are shown
in Figure 20.
Scheme 52
Figure 20. Compounds obtained in Ni-catalyzed reactions.
with an 83% yield, which matched the yield obtained by their Pd(II)-catalyzed intermolecular C−H thiolation with a
colleagues. Therefore, it was also possible to lower the directing group was performed for the first time independently
temperature from 140 to 120 °C.111 by Nishihara290 and Shen and co-workers.291 It is known that
According to the proposed mechanism, reductive elimi- the presence of the CF3 group is important for the production
nation occurs from both the palladacycle with Pd(IV) and the of many drugs. Xu and Shen conducted trifluoromethylth-
palladacycle with Pd(II), whereas DMSO acts as an oxidizing iolation of an arene with a directing group by using an
agent. electrophilic sulfenylating agent with an N-SCF3 group in
An intramolecular reaction catalyzed by Pd(OAc)2 includes acetic acid (Scheme 54, A).291
the activation of the C−H bond and cyclization with the Direct trifluoromethylthiolation was selectively performed
participation of the “masked” SH group. The reaction allowed by Huang and co-workers at the ortho position of 2-
the synthesis of a large series of sulfur-containing benzohetero- phenylpyridine by using AgSCF3 in the presence of acetic
cycles, which is of interest for the synthesis of semiconducting acid and Selectfluor.292 Direct phenylselenylation of arenes and
materials (Figure 19).287 heteroarenes in a Pd-catalyzed reaction with pyridine as a
Scheme 54
Figure 19. Compounds obtained via Pd(II)-catalyzed C−H activation

and cyclization.
A Pd-catalyzed synthesis of dibenzothiophenes from

benzylphenyl sulfoxides was described. This interesting
reaction required the presence of aryl iodide (4-FC6H4I) and
an oxidizing agent and included the stages of C−H activation
and Pummerer rearrangement (Scheme 53, A).288
A preparation of new sulfur-containing compounds via a
Pd(II)-catalyzed reaction of thiophene with alkynes in the
presence of Cu(OAc)2 as an oxidizing agent that proceeded
with the rupture of C−S and C−H bonds was described
(Scheme 53, B).289
Chem. Rev. 2022, 122, 16110−16293
directing group and a similar electrophilic reagent was carried Scheme 56

out in water (Scheme 54, B).293
Dong and co-workers used pyridine as a directing group in
Pd(II)-catalyzed reactions to produce sulfones (Scheme 55,
Scheme 55
A).294 The authors provided evidence of the conversion of

Pd(II) to Pd(IV) upon this reaction.295 However, the same
reaction of 2-phenylpyridine proceeded at the meta-position
when catalyzed by a ruthenium complex.296 It was assumed Scheme 57
that the formed metallocene (B, Figure 21) directed an
electrophilic attack at the para-position (at meta with respect
to pyridine).
Figure 21. Ruthenium complex B after metalation.
Nishihara and co-workers carried out a reaction of arenes

with disulfides or thiols in which ortho selectivity was provided N-(Arylthio)benzamide is a sulfenylating and oxidizing
by DG: 2-(3-methyl)pyridyl, 2-quinolyl, 2-pyrimidyl, or agent. Zhang and Zhang and co-workers performed mono-
bidentate 8-aminoquinoline, although the optimization was and disulfenylation of 2-phenylpyridines in high yields.301
performed with 2-phenylpyridine. At high temperatures, Examples of disulfenylation in an excess of a sulfenylating
thiolated products were obtained in good yields (Scheme 55, agent are given in Scheme 58.
B).290 With dialkyl disulfides, the yield dropped sharply. The pyridine-directing group in 2-aryloxypyridines allows
This methodology was used in Pd-catalyzed selenylation palladium-catalyzed ortho-sulfonylation by ArSO2Cl to be
with the participation of RSeH or RSeSeR297 (Scheme 55, C). carried out (Scheme 59, A). The authors proposed a
When using aminoquinoline as a directing group, the mechanism involving Pd(IV).302
quantitative yield was approached (Scheme 56, A), and the
directing group could be removed easily. Similar reactions were Scheme 58
performed with other arenes and heteroarenes with the
participation of disulfides and diselenides by using double
palladium and copper catalysis (Scheme 56, B).290,298
When using 8-aminoquinoline as a directing group, direct
sulfonylation at the C(sp3)−H bond was carried out under the
action of sodium sulfinate (Scheme 56, C).299
It should be noted that 8-aminoquinoline as DG allows the
introduction of various nucleophiles into the ortho-position of
arenes by using various metals.300 Efficient Pd(II)-catalyzed
ortho-selenylation was carried out for arylacetic amide via ortho
C−H bond activation with diaryl diselenides or phenylselenyl
chloride (Scheme 57).95 The addition of HOTf improves the
product yield.
Chem. Rev. 2022, 122, 16110−16293
Scheme 59 Scheme 60
In the reaction of N-arylsulfonamide with diaryldisulfides

and diselenides, Pd(II) catalyzed the chalcogenation reaction
to the ortho position as a result of a weak coordination
interaction of Pd−O. Cu(OAc)2 was used as an oxidizing
agent. A large series of selenium derivatives with a wide range
of substituents in both reagents were obtained under the
optimized conditions for Ph2Se2 and Me2Se2 (Scheme 59,
B).303 A similar reaction with R2S2 proceeded with yields from
44% to 95% (nine new compounds were obtained). source of S (Se) (Scheme 61). For 2-substituted thiophenes
The carbonyl group can be used as a DG. Ortho-CH- and N-methylindole, the reaction proceeded with good yields
selenylation of benzaldehyde, catalyzed by Pd(II) with Cu(II)
as an oxidizing agent, was carried out under the action of Scheme 61
Ar2Se2 upon using benzidine as a “transient directing group”
(TDG) (Scheme 59, C).304 With heterocyclic aldehydes, the
yield is lower, and with furfural and N-methylpyrrole aldehyde,
the reaction does not proceed. The method undoubtedly
deserves attention since it uses a recyclable leaving group and
allows the reaction to be carried out with arenes containing
EWG (CHO).
Palladium(II)-catalyzed thiotrifluoromethylation of primary
and secondary C(sp3)−H bonds in 8-aminoquinoline deriva-
tives under the action of various donors of the SCF3 group (of
which NSCF3-phthalimide and N-methyl-N-
(trifluoromethylthio)aniline were the most selective com-
pounds) was carried out (Scheme 60, A).305 Nevertheless,
these reactions proceeded with moderate yields (8−53%).
There are other examples of Pd-catalyzed reactions that allow
and high selectivity. Benzo[b]thiophenes and benzofuran
chalcogenation of the C(sp3)−H bond (Scheme 60, B).306
reacted significantly worse. However, a 2-substituted furan
Pd-catalyzed picolinamide-directed chalcogenation of ben-
produced the thiolation product in quantitative yield. Phenyl-
zilic C(sp3)−H under the action of Ar2Y2 (Y = S, Se) was
selenylation reactions proceeded in a similar manner.
carried out (Scheme 60, C).307 Ditert-butylperoxide (DTBP)
was used as an oxidizing agent. Under these conditions, 4.2. Copper-Catalyzed Transformations
Pd(OAc)2 showed higher efficiency than Co, Ni, and Cu salts. 4.2.1. Modern Ullmann Chemistry. 4.2.1.1. Formation
The radical mechanism of the reaction with the participation of of C(sp2)−S (Se) Bonds with Thiols. Although Ullmann
ArS was confirmed by its upregulation upon the addition of coupling in its present form is one of the most efficient
TEMPO. methods for obtaining a carbon−heteroatom bond,22 the
Another variant of the preparation of benzylaryl sulfides was mechanism of the copper-catalyzed reaction, in contrast to the
realized via benzylation of the thiol group. Selective palladium-catalyzed Buchwald−Hartwig reactions, remains
benzylation at the S−H bond in 2-mercaptobenzoic acid is controversial.42,53,310
achieved by using benzyl alcohols in water upon Pd(OAc)2/ We have already noted the special role of ligands in copper-
TPPMS catalysis (yield up to 98%; TPPMS, sodium catalyzed reactions; nevertheless, reactions of C−S bond
diphenylphosphinobenzene-3-sulfonate) (Scheme 60, D).308 formation catalyzed by “ligand-free” copper compounds (salts
Direct sulfenylation and selenylation of the CH bond in or oxides) are known,311 but they are usually carried out in
heteroarenes can proceed upon using heterogeneous catalysts. solvents capable of coordination with copper. However, in all
Glorius and co-workers309 carried out the process by using Pd/ cases, the use of ligands facilitates the progress of the reaction.
Al2O3 in the presence of CuCl2 and disulfide (diselenide) as a DFT comparisons of such reactions show that the ligand
Chem. Rev. 2022, 122, 16110−16293
facilitates the cross-coupling step by lowering the activation

barrier312 and promotes the dissociation of the C−Br bond.313
After the publication of works in which the existence of
Cu(III) was proven and the possibility of participation of By using the reaction of diiodobenzene with thiol, Wan and
Cu(III) complexes in the catalytic cycle of S-cross-coupling co-workers solved the problem of obtaining a monosubstituted
was established, the viewpoint that all these reactions product from diiodarene with the further possibility of using
proceeded in this way became predominant. There are works the C(sp2)−I bond.317 Monosubstituted diaryl sulfide was
in which, according to the authors, the coupling mechanism selectively formed in the CuI/L-Cs2CO3−DMSO system
includes the formation of Cu(IV).314 However, it is most under optimized conditions at 100 °C. The obtained
difficult to combine these concepts with the reactions catalyzed compounds were introduced into the Suzuki−Miaura reaction
by “ligandless” copper salts and oxides (Cu2O and CuO) and, and into the reaction with azoles (Scheme 62, D).
especially, by copper nanoparticles, for which it is customary to In the reaction of Cu-catalyzed C−S-cross-coupling of ArI
produce a picture corresponding to palladium catalysis Pd (0) with arylthiols, the well-known ligand 8-hydroxyquinoline-N-
⇄ Pd (II). Therefore, we avoid discussing the mechanism and oxide was used (Scheme 62, E).318 The reactions are tolerant
present only the viewpoint of the authors. The same applies to to various functional groups.
the elucidation of the true nature of the reaction and the role Chen, Miao, and co-workers tested a series of interesting
of radical processes. Of course, the formation of sulfones with N,N′-dioxide ligands in a cross-coupling reaction involving
the participation of RSO2Cl and RSO2Na, catalyzed by the amines, phenols, and thiophenols. With the best of them, the
same copper catalysts, for which the participation of the reactions proceeded with high yields under relatively mild
Cu(III) complex, although formed differently, is also assumed, conditions (Scheme 62, F).319 Hematoxylin, which is obtained
appears strange. We think that all these suggestions will be from natural raw materials by extraction from Lignum Sappan,
revised repeatedly in the future. was proposed as an efficient and “green” ligand for the S-
In copper-catalyzed cross-coupling, similar to palladium- arylation of thiols (Scheme 62, G).320 p-NO2C6H4Br produced
catalyzed reactions, the simplest method for the preparation of the product with a 50% yield.
diaryl sulfides is the reaction of an aryl halide with aromatic Racemic diazaphospholane proved to be another efficient
thiols. The issues of this reaction, in addition to the disgusting ligand that performed better than L-proline, triphenylphos-
odor of thiols, are their easy oxidation, resulting in the phine, or DMEDA (Scheme 62, H).321 Oxalic diamides were
formation of disulfide, and, of course, the choice of ligand. proposed to be used as ligands in the cross-coupling of aryl
Practice has shown that there are many such ligands, and they
halides with thiophenols. L1 and L2 were the best ligands
are quite cheap and easy to use (Figure 22).
(Scheme 62, I).322
Varying the substituents in ArSH led to changes in the yield
from 56 to 95%. With alkyl thiols, the yields remained high
(66−95%). The reaction with ArCl required higher temper-
atures (120−130 °C), but the yields of the model reaction with
L2 were good (77%) and varied over a wide range (33−95%).
Obtaining diaryl sulfides via the cross-coupling reaction of
aryl iodides with thiols under microwave irradiation allows the
Figure 22. Ligands for copper catalysis. reaction to be carried out under milder conditions with an
increase in the yield. It was shown that varying the substituents
in both reagents in the CuI/neocuproine (L)-K3PO4 system in
nBuOH led to reactions with yields from 94% to 98% (Figure
However, new ligands for the Ullmann reaction appear quite 23).323
regularly, making catalysis even more efficient and selective. Condensation of aryl iodide and bromide with thiophenol
Thus, Sekar and co-workers suggested using the Cu(OTf)2− catalyzed by CuI/trans-1,2-cyclohexanediol with various
BINAM catalytic system in Ullmann cross-coupling (Scheme substituents in ArHal was carried out under microwave
62, A). Aryl iodides react in high yields (14 examples, 87− irradiation (Scheme 62, J).324
97%), and aryl bromides react in good yields (11 examples, The S-cross-coupling reaction catalyzed by CuI/L-proline in
53−90%). Electron-withdrawing groups containing aryl halides aqueous media (aqueous two-phase system) demonstrates an
and tosylates react without a catalyst.315 Exceptionally high advantage over the Pd-catalyzed reaction. Even electron-
yields were obtained in the reaction of ArI with PhSH when deficient chlorides are involved in the reaction (Scheme 62,
using CuI with a tridentate ligand (Tpm*) (Scheme 62, B).316 K).325
Zheng and co-workers proposed a successful C−S-cross- A well-chosen ligand allows high-yield S-arylation not only
coupling protocol involving aryl halides and aromatic and for aryl bromides but also for aryl chlorides with EWG, but
aliphatic thiols catalyzed by Cu(OAc)2·H2O.314 Upon testing only upon increasing the temperature and duration of the
common ligands and compiling their activity series, they found reaction (Scheme 62, L).326 Symmetrical and unsymmetrical
2,2′-bisimidazole to be the best. Among the various copper bisthioethers were obtained in high yields.
salts, Cu(OAc)2·H2O showed the best results with this ligand The use of N-heterocyclic carbene complexes, the best of
(Scheme 62, C). 2-Bromonaphthalene and 2-bromopyridine which was IMesCuCl, in the reaction of aryl iodides with
do not react; however, these aryl halides produce good yields thiophenol in the presence of a strong base resulted in yields
with alkyl thiols, for example, with C5H11SH (the product is comparable to those obtained in the above-discussed reactions
obtained in 95% yield). Aryl halides also form high-yield but at a higher temperature (Scheme 62, M).327 A new ligand
products with the following thiols: was successfully used in Cu(I)-catalyzed reactions of S-cross-
Chem. Rev. 2022, 122, 16110−16293
Scheme 62
Chem. Rev. 2022, 122, 16110−16293
Scheme 62. continued
A convenient protocol for thioetherification of aryl and

heteroaryl halides is described in.329 The reaction of p-
methoxyphenyl iodide and other iodides with thiophenol (21
examples) catalyzed by CuI (5 mol %)/DABCO (10 mol %,
Figure 23. Structure of neocuproine. 1,4-diazabicyclo[2.2.2]octane) (K2CO3, 120 °C, 12 h)
proceeded with high yields. In the case of bromides, the yields
coupling and selenation of alkynes (Scheme 62, N (1) and were 49−78%. The authors considered a mechanism involving
(2)).328 Cu(III).
Chem. Rev. 2022, 122, 16110−16293
The possibility of a mechanism in which the catalytic cycle Scheme 65

involved Cu(I) ⇄ Cu(III) transitions330 was proven by the
authors,331 who showed that the Cu(III) complex reacted with
HS(Se)R to form products with a C−S or C−Se bond and that
this reaction could be carried out in catalytic form (Scheme 63
(1) and (2), respectively).
Scheme 63
The production of vinyl sulfides via the Ullmann-type

process allows avoidance of the issues with regioselectivity that
arise upon the addition of thiols to alkynes. The reactions of
vinyl chlorides with RSH are catalyzed by Cu2O/1,10-phen
(KOH, dioxane) at 110 °C. For example, (cyclohexylidene-
methyl)(dodecyl)sulfane is obtained in 93% yield. The
reactions of styryl bromides and chlorides do not require
catalysis.336
The reaction of styryl iodide with aromatic thiols proceeds
with simultaneous hydroxylation of the benzene ring (Scheme
66, A).337 The reaction of ortho-dihalides with ortho-amino-
benzothiophenols using CuI as a catalyst leads to the
production of substituted phenothiazines. In this case, it can
be assumed that DMSO acts as the ligand (Scheme 66, B).338
Hartwig and co-workers carried out the reaction of p-tolyl Fused thiazoles are obtained via S,N-diarylation catalyzed by
iodide with thiolate complexes of copper with phenanthroline Cu/1,10-phen or Cu/proline in DMF or H2O (Scheme 66,
ligands in DMSO. The reaction proceeded very fast and with a C).339 In the CuI/phen-catalyzed reaction of ortho-dihalides
high yield (Scheme 64).332 with 2-mercaptobenzimidazoles, benzo[d]benzo[4,5]imidazo-
[2,1-b]thiazole derivatives were obtained as a product of the
Scheme 64 domino reaction (Scheme 66, D).340
In continuation of their studies, Shen and Zhang carried out
the reaction (Scheme 66, E) catalyzed by Cu and Pd in which
annulation with the formation of C−S and C−N bonds
occurred at the beginning, and then the formation of a C−C
bond took place in the reaction with aryl halide as a result of
palladation at the C−H bond under the action of ArPd(II)-
X.341
The CuI/1,10-Phen-catalyzed S-cross-coupling reaction
The data obtained are consistent with a mechanism between 1,8-diiodonaphthalene and 2-mercaptobenzimidazoles
involving copper thiolate complexes. The authors argue against or 2-thiouracils produced benzo[4,5]imidazo[2,1-b]naphtho-
the participation of aryl radicals in the reaction. [1,8-de][1,3]thiazines and 11H-naphtho[1,8-de]pyrimido[2,1-
Hui and co-workers carried out the arylation of various b][1,3]thiazin-11-ones (Scheme 66, F).342 The model reaction
heterocyclic thiols with aryl iodides catalyzed by Cu(I)/1,10- with 1,8-dibromonaphthalene produced a 24% yield. The
phen, which proceeded with high yields at 120 °C (Scheme 65, introduction of a 6-nitro group into mercaptobenzimidazole
A).333 Below are examples of the synthesized compounds. Of rendered the compound inert (0% with both reagents).
the two possibilities of arylation at S- or at N- in the reaction of It should be noted that similar annelation reactions with the
2-mercaptobenzimidazole catalyzed by CuI/1,10-Phen, the formation of C(sp2)−S and C(sp2)−N bonds were performed
reaction proceeds via the S-arylation pathway (Scheme 65, earlier for mercaptobenzimidazole with ortho-bromobenzyl
B).334 In the copper-catalyzed reaction of heteroarylthiols with bromides.343 The reaction of 2-iodaniline with 2-mercaptoa-
low nucleophilicity, the selection of the desired ligand plays an cetate yielded 1,4-benzothiazin-3-ones (Scheme 66, G).344
especially important role (Scheme 65, C).335 Bis(2-pyridyl)diselenoethers with different bridges can serve
In N-methyl-2-pyrrolidone (NMP), which can act as a as ligands in the Ullmann cross-coupling, and the best results
chelator, the reaction of ArI with ArSH proceeds under were obtained with the diselen ligand with four methylene
catalysis by ligand-free CuI (K2CO3). However, alkyl thiols units.345 A large series (15 compounds) were synthesized via
react poorly under these conditions.311 the reaction of aryl/heteroaryl iodides, including di-ortho-
Chem. Rev. 2022, 122, 16110−16293
Scheme 66
substituted iodides, which produced high yields (78−99%)

with thiols, while with alkyl thiols, the yields decreased.
Chem. Rev. 2022, 122, 16110−16293
Scheme 67
Scheme 68
Scheme 69
Chem. Rev. 2022, 122, 16110−16293
Scheme 70
Chem. Rev. 2022, 122, 16110−16293
Scheme 71
example of divergent regioselectivity controlled by the catalytic

system and conditions is given in Scheme 69.
CuI without a ligand was an excellent catalyst for the
reaction of 2-mercaptobenzothiazoles with aryl iodides in
water and provided very good yields, but with aryl bromides,
the reaction produced poor yields. Similar derivatives of
benzoxazole and benzimidazole did not enter the reaction
(Scheme 69, B).110
Kumar and co-workers84 studied the formation of C−S
bonds in a copper-mediated reaction without a ligand in the
“green”, recyclable solvent glycerol, which could serve as a
ligand for CuI (Scheme 70, A). However, the yield in the
reaction with aryl bromides decreases (33−83%, Ph2S − 58%),
However, many reactions can be carried out without a whereas among aryl chlorides, only p-NO2C6H4Cl is active.
ligand. This fact is especially important since copper, due to its With isomeric styryl bromides, the reaction of diselenides
relatively low cost and low toxicity of its salts and oxides, has and ditellurides in the presence of zinc also proceeds under the
become the most popular catalyst in cross-coupling reactions; catalysis of “ligandless” CuI in glycerol (Scheme 70, B).349
therefore, such catalysts can be in demand in industry. As Ligand-free cross-coupling of aryl iodides with aromatic,
shown below, ligand-free CuI, Cu2O, and CuO are usually heteroaromatic, and aliphatic thiols was carried out in DMF
used as catalysts in reactions with aryl iodides and in solvents with an immobilized KF/Al2O3 base. In the case of aromatic
capable of copper coordination, such as DMSO.346 iodides, the reaction proceeded with high yields. In the case of
Chae and co-workers carried out a broad study of the aliphatic thioles, the yields varied from good to high (Scheme
copper-catalyzed Ullmann-type process with dithiolates.347 1,2- 70, C).350
Ethanedithiol and 1,4-butanedithiol with aryl iodides, aryl Fluorescent derivatives of naphthalimide have applications
bromides, and electron-deficient aryl chlorides produced aryl in various fields. For the 4-bromo derivative, a CuI-catalyzed
thiols in good yields (Scheme 67). The rest of the dithiols also thiolation with benzylthiols was carried out in water in the
gave monosubstituted products in good yields. Symmetric presence of the solid KF/Al2O3 base (Scheme 70, D).351
diaryl sulfides can be obtained in an excess of aryl halide, Microwave irradiation allows the Ullmann-type process
whereas upon addition of a new aryl halide to the thiol, catalyzed by CuO in water to be carried out in a short period
asymmetric diaryl sulfides can be obtained. of time (Scheme 70, E).352 An interesting copper-promoted
The intramolecular reaction of 1-ortho-alkynyl bromoben- reaction of disulfide with thiophenols leading to the formation
zene with 1,2-ethanedithiol was carried out under the same of a mixed sulfide is demonstrated by the example of 1,2-
conditions to obtain 2-substituted benzothiophenes (Scheme di(pyrimidin-2-yl)disulfides (Scheme 70, F).353 Arylsulfanyla-
68). tion and arylselanylation of iodine derivatives of pyrimidine
The arylation of 2-mercaptobenzothiazole, catalyzed by and 7-deazapurine nucleosides and nucleotides, mediated by
copper in PEG400, can proceed selectively at the S or N CuI/bpy, for example, under the action of disulfides and
atoms. The regioselectivity of the reaction is determined by the diselenides, were described (Scheme 70, G).354
type of copper catalysis, base, and most importantly the Symmetrical and unsymmetrical diaryl sulfides are produced
reaction temperature.348 CuI-NaOH-50 °C is required for in good yields under optimized conditions in the reaction of
arylation at sulfur, and CuO-KOH-140 °C is required for the aryl iodides with diaryl(dialkyl)disulfides and diaryldiselenides
formation of a C−N bond (Scheme 69, A). An interesting in DMSO under catalysis by CuI with 4′-(4-methoxyphenyl)
Chem. Rev. 2022, 122, 16110−16293
2,2′:6′,2″-terpyridine (Mtpy) at 110 °C (Scheme 70, H).355 Scheme 73

However, the yields drop upon using aryl bromides and aryl
chlorides.
Fu, Peters, and co-workers demonstrated that photoinduced
copper-catalyzed reactions of aryl halides and thiols proceeded
at a very low temperature of 0 °C (Scheme 71, A).356,357 The
reactions can be carried out even at −40 °C, as shown by
Scheme 71, B. Even chlorides react under standard conditions
(Scheme 71, C).
A reaction mechanism was proposed in which, in contrast to Na2S2O3 is the source of sulfur, allows unsymmetrical sulfides
classical photoredox catalysis, the copper complex participated to be obtained with a high yield (Scheme 74, A).361
both in electron transfer and in the key step of the formation of The diazonium group as a leaving group is used in a three-
the C−S bond (Figure 24). component reaction with inodorous stable Na2S2O3 as a
sulfurating reagent. A very large series of thioesters were
obtained under the optimized conditions with moderate to
high yields. The diazo component was formed in situ, and the
reaction itself could be carried out in preparative quantities
(for example, 2.30 g of p-MeOC6H4SBn was obtained with a
yield of 99%). The proposed radical reaction mechanism
distinguished the behavior of this sulfenylating agent from
others, such as Na2S, S8, RSH, and R2S2 (Scheme 74, B).362
Aryldiazonium salt in a CuSCN-catalyzed three-component
reaction with the Ruppert−Prakash reagent as a source of the
CF3 group and sodium thiocyanate as a sulfur source produced
trifluoromethylthioarene via the Sandmeyer-type reaction with
moderate to high yields at room temperature (Scheme 75,
A).363 According to the proposed mechanism, ArSCN is
formed, in which the CN− anion is exchanged for the CF3
group. The reaction is inhibited by the addition of TEMPO.
Upon changing the reaction conditions and the catalyst
Figure 24. Role of copper in the photoredox reaction of thiolation.
nature, Cu(I)-catalyzed Sandmeyer reactions of aryldiazonium
salts with sodium trifluoromethylsulfinate result in the
Recently, the authors358 have shown by a large number of predominant formation of products of trifluoromethylsulfony-
examples that symmetric and unsymmetrical sulfides can be lation or trifluoromethylation (Scheme 75, B).364
obtained from the corresponding disulfides (diaryl- or The Cu(NO3)2-catalyzed oxidative coupling of hydrazines
arylbenzyl) via catalysis by CuI/1,10-Phen (DMSO, K2CO3, with thiols, in contrast to a similar reaction catalyzed by
120 °C) (Scheme 72). palladium, was carried out in water using a surfactant, which
was also a ligand. A study of such phen- or bpy-based PEG
Scheme 72 ligands demonstrated that L provided the best results (Scheme
75, C).365 With rare exceptions, the yields for various
hydrazines and thiols are high. The solution retains catalytic
activity even after five cycles. By the example of phenyl-
hydrazine and 7-methoxybenzothiol, the scalability of the
reaction was demonstrated: 1 g of sulfide was obtained in a
95% yield.
Decarboxylation of acids, leading to the formation of an
Single examples demonstrated that such dechalcogenation organometallic compound, can be considered a method of
was also possible for diaryldiselenides and diarylditellurides. alternative activation of the CH bond. However, only recently
Interestingly, the decomposition of p-MeO-PhSSePh resulted has it been used to obtain diaryl sulfides.45,366
in the production of p-MeOPhSePh (63%). Using substituted ortho-nitrobenzoic acids as an example, a
Chlorine-containing electron-deficient aromatic (and heter- reaction with aromatic and heteroaromatic thiols catalyzed by
oaromatic) halides exchange chlorine for a selenyl group under CuI in the presence of oxygen as an oxidizing agent was carried
the action of selenolate obtained by the reduction of out (Scheme 76, A).366 With heteroaromatic acids, the yields
diselenides with dithiothreitol (DTT) in the presence of a vary from moderate to good. The reaction of perfluorobenzoic
base.359 acid under these conditions proceeds simultaneously as
Below, we discuss the reactions in which arenes with decarboxylation-thiolation and SNAr parasubstitution, produc-
different leaving groups are involved instead of aryl halides. ing p-(PhS)2C6F4 in 70% yield.
An interesting alternative to Ullmann’s S-cross-coupling is a The decarboxylation of aromatic carboxylate salts in DMSO,
Cu-catalyzed reaction of nitroarenes with thiols. Shinde and catalyzed by CuBr/1,10-Phen in the presence of Zn(OTf)2,
co-workers proposed high-yield conditions for such a reaction was carried out to obtain a thiomethylation product (Scheme
by using CuI without a ligand (Scheme 73).360 76, B).91
A trimolecular copper-catalyzed reaction with nitroarenes A supported CuI-catalyzed three-component reaction of
and nitroheteroarenes, where NO2 is the leaving group and aromatic acid with elemental sulfur and aryl halides producing
Chem. Rev. 2022, 122, 16110−16293
Scheme 74
Scheme 75
unsymmetrical diaryl sulfides was described (Scheme 76, to the previous authors’ work,370 where PhSO2S(Se)R was
C).367 used) (Scheme 76, D (1)). In the second case, cyclic amines
Interesting Cu(OAc)2-catalyzed cascade 3-component re- and molecular sulfur participate in the reaction (Scheme 76, D
actions involving decarboxylation of propiolic or acrylic acids (2)).369
are described in refs 368 and 369. In the first case, the reaction Useful bioactive diaryl and arylmethyl selenides are obtained
proceeded in the presence of disulfides and diselenides (similar via copper-catalyzed decarboxylative selenylation in the
Chem. Rev. 2022, 122, 16110−16293
Scheme 76
reaction of aromatic carboxylic acids with diaryl and A method for the preparation of aryl and alkyl trifluor-
arylmethyldiselenides (Scheme 76, E).371 omethyl sulfides via a three-component reaction was proposed
Of note, there are a significant number of reactions catalyzed (Scheme 78, B).375 The reaction with ortho-iodo-tert-
by complexes of transition metals that proceed via pathways butylbenzene does not proceed. The reaction proceeds via
differing from those considered in this review. the formation of S-aryl(alkyl)sulfothioate, which then interacts
A good example is the CuNP-catalyzed synthesis of 2- with CF3SiMe3. In the case of aryl iodides, both stages are
amino-3,5-dicyano-6-sulfanylpyridine in a three-component catalyzed by Cu(I). Various ketones with an α-trifluorome-
reaction (Scheme 77, A).372 The production of esters thylthio group at C(sp3) were obtained in a three-component
(thioesters) from aromatic or aliphatic aldehydes with reaction catalyzed by Cu(OTf)2/1,10-Phen (Scheme 78,
aryl(alkyl)thiols occurs under the catalysis of CuI and TBHP C).376
as oxidizing agents in water. Thioesters are formed in moderate The Bunte salt was investigated377 in the introduction of a
to good and even high yields (Scheme 77, B).373 fluoromethylthio group into the aromatic ring in the reaction
4.2.1.2. Sulfur Sources Other than Thiols. The most with amines (in situ ArN2X) and thiols (Scheme 78, D). The
convenient thiol substituent is its salt, which is especially reaction of ArI with nBuTeLi, catalyzed by CuI/DMF in THF
important for gaseous compounds. A copper salt was used in at 80 °C, proceeds with a good yield of arylalkyl tellurides, and
the ArI reaction to introduce a CF3S group into an aromatic or PhTeLi reacts with very moderate yields; however, the reaction
heteroaromatic ring (Scheme 78, A).374 Naturally, this salt acts with ArBr does not proceed at all.378
as a reagent and catalyst. Activated ArBr participated in the An interesting protocol was proposed by Feng and co-
reaction. workers for the production of thiophenols via the action of
Chem. Rev. 2022, 122, 16110−16293
Scheme 77
elemental sulfur on ArX catalyzed by nano-CuI in water Such one-pot intramolecular thiolation was independently
(Scheme 79).379 In the case of ArI, the yields were very high; performed by Punniyamurthy383 (1) and Kumar384 (2) and co-
however, for ArBr, the presence of EWG in the molecule was workers in the CuX (X = I, Cl)-catalyzed synthesis of
required, as well as an increase in the catalyst concentration benzo[d]isothiazol-3(2H)-ones using powdered sulfur
and temperature (80 °C). (Scheme 81, A).
Taniguchi carried out the synthesis of symmetric diary- An interesting reaction for obtaining benzo[1,4,2]dithiazine
lchalcogenides via the reaction of aryl iodides with elemental 1,1-dioxides and benzo[1,4,2]thiaselenazine 1,1-dioxides from
chalcogenes (S, Se, Te) upon CuI-bpy catalysis and the functionalized ynamides was carried out with elemental sulfur
addition of reducing agents (Scheme 80, A).380 The tellurium and selenium using the Ullmann cross-coupling step (Scheme
derivative was obtained in a low yield (25%). According to the 81, B).385
author, the reaction of chalcogenides proceeded via the The Cu(I)-catalyzed reaction of 2-(2-iodophenyl)imidazo-
formation of the copper salt CuYM. [1,2-a]pyridine with elemental selenium proceeds intramolec-
Symmetric diaryl selenides were also obtained via the Cu2O- ularly with the formation of fused benzo[b]selenophene
catalyzed reaction of aryl iodide with elemental selenium. This imidazo[1,2-a]pyridine (R = H, 87%). Other chalcogenides
reaction proceeded with a yield of 92% in 18 h, and upon either do not react or produce a mixture of products with the
microwave irradiation, it stopped with a yield of 93% in 1 h predominant formation of dichalcogenide (Scheme 81, C).386
(Scheme 80, B).381 Although the reaction mechanism is quite A simple and efficient way to synthesize 2-substituted
complex, the method itself is simple and efficient. The benzothiazoles, which may include drug analogues, in
supposed mechanism is given in Figure 25. moderate to high yields is the Cu(II)-catalyzed three-
Chen and co-workers demonstrated that the selectivity of component reaction of 2-iodoanilines with sulfur and benzyl-
the ArX reaction with sulfur powder was controlled by the (alkyl)amines (Scheme 81, D).387 A three-component reaction
base. The strong base produced predominantly Ar2S, while the of ortho-iodoaniline with aldehyde and sulfur powder in water
weak base produced ArSSAr. Moreover, a strong base produces substituted benzothiazoles in good to high yields
converted the disulfide to mono (Ar2S2 → Ar2S).382 (Scheme 81, E).388 The ArSeCu nucleophile that forms upon
The [Cu]/1,10-phen-catalyzed reaction of aryl iodides with the interaction of ArI and Se under Cu(I) catalysis opens the
elemental sulfur or selenium in H2O afforded the correspond- oxirane cycle (Scheme 81, F).389 Cu(II)-catalyzed diarylation
ing diaryldisulfides and diaryldiselenide in high yields (up to of selenium in the presence of azole and aryl iodide proceeds
96% and 92%, respectively) (Scheme 80, C).372 via the stages of ArSeCuX formation and CH metalation
A recently published review is devoted to the use of (Scheme 81, G).390 In the proposed reaction mechanism, an
molecular sulfur in the synthesis of sulfur-containing hetero- intermediate with Cu(III) is formed as a result of
cycles via C−H activation.78 disproportionation of a complex with Cu(II) (Figure 26).
Intramolecular thiolation, carried out in a tandem cross- Interesting CuI-catalyzed rearrangements that occur under
coupling/heterocyclization reaction, is an excellent strategy for the action of sulfur or selenium on 2-bromo-benzothioamides
the preparation of sulfur-containing heterocycles.28 are described, and they result in the formation of benzodithiols
Chem. Rev. 2022, 122, 16110−16293
Scheme 78
Scheme 79 Using this sulfur source, Sekar and co-workers synthesized

thioflavanones from ortho-iodochalcones. The reaction was
catalyzed by “ligandless” Cu(OAc)2 and produced a large
series of compounds (Scheme 82, C).393
Upon changing the position of the double bond and the
carbonyl group, the authors obtained 2-acylbenzo[b]-
thiophenes under the same conditions. Simirlarly to ref 393,
Ullmann cross-coupling followed by functionalization of the α-
or benzothioselenols. Without the addition of sulfur or CH bond with the formation of the second C(sp2)−S bond
selenium, dibenzodithiocines are formed (Scheme 81, H).391 occurred in the reaction (Scheme 82, D).394
Potassium ethyl xanthogenate can serve as a source of sulfur The preparation of 2-acetylthienopyridine was done using
in the reaction with ArI catalyzed by copper (Cu(OAc)2/L xanthate in the reaction with o-propynol fluoropyridine
(BINAM)) (Scheme 82, A).392
In continuation of their research, Sekar and co-workers109 (Scheme 82, E).395 The reaction includes nucleophilic
carried out one-pot reactions to synthesize benzothiazoles and aromatic substitution followed by cyclization due to the S-
benzothiophenes using potassium ethyl xanthogenate (Scheme nucleophilic attack at the triple bond activated by coordination
82, B). with copper.
Chem. Rev. 2022, 122, 16110−16293
Scheme 80
thiolation and Michael addition to a multiple bond followed by

aldol condensation, was carried out by Sekar and co-
workers.396 The reaction produced thiochromenes (Scheme
82, F).
Ho and co-workers carried out CuI/1,10-Phen-catalyzed
cross-coupling of aryl and heteroaryl iodides with thiobenzoic
acid (Scheme 83, A).397 The resulting aryl/heteroaryl
thiobenzoates were oxidized in the presence of trichloroiso-
cyanuric acid (TCCA) and benzyltrimethylammonium chlor-
ide (BnMe3NCl), yielding the corresponding sulfonyl chlorides
(Ar(Het)SO2Cl).
This reaction was applied to the synthesis of thiophenyla-
lanines and thiophenylalanine-containing peptides (Scheme
83, B).398
It was shown that the preparation of S-phenyl thioacetate via
the reaction of aryl iodides with potassium thioacetate
proceeded best under CuI/1,10-Phen catalysis (12 examples).
Figure 25. Cu2O-catalyzed symmetrical diaryl selenide formation. In most cases, convenient heating (100 °C, 24 h) produced
better results than MW irradiation (110 and 140 °C, 2 h)
(Scheme 83, C).399 Upon microwave irradiation, the reaction
time decreased from 24 to 2 h.
Peñeń ̃ory and Andrada and co-workers studied the reaction
of aryl halides with potassium thioacetate (Scheme 83, D).400
The authors studied the reaction mechanism. A radical clock
test was performed, and the result was negative. Therefore, the
authors believe that an unstable Cu(III) complex is involved in
the reaction, and the classical scheme of oxidative addition/
reductive elimination is considered.
The one-pot methodology, where the formation of the C−S
bond is a key step followed by the addition step (and migration
of the acetyl group) in the preparation of benzothiazines, is
described in ref 401 (Scheme 83, E).
Figure 26. Cu(II)-catalyzed formation of diarylselenides via C−H As almost simultaneously shown by two groups, Shimizu and
activation with the participation of Cu(III). co-workers402 and Jiang and co-workers,403 the usage of diaryl
iodonium salts in copper-catalyzed reactions allowed double S-
An interesting Cu(II)-catalyzed domino reaction involving arylation. Both groups found that potassium thioacetate was
potassium ethyl xanthogenate as a source of sulfur, including the best source of sulfur in these reactions.
Chem. Rev. 2022, 122, 16110−16293
Scheme 81
Chem. Rev. 2022, 122, 16110−16293
Scheme 82
In the first case, the reaction with dibenziodolium triflates obtained precisely with CuCl2−KSAc. Therefore, they were
was intramolecular, and different systems were compared: used in the reaction under these conditions (Scheme 84, A).402
Pd2(dba)3 or Pd(OAc)2−K2S and various copper salts, as well In the second case, the reaction was intermolecular (Scheme
as different sources of sulfur; however, >99% yield was 84, B).403 The established conditions were applied to the
Chem. Rev. 2022, 122, 16110−16293
Scheme 83
intramolecular variant, where the replacement of iodine with nyliminophosphrane and isocyanate catalyzed by Cu(OTf)2 in
sulfur was also successful (Scheme 84, C). The reaction allows DMF was carried out (Scheme 86, A).410
sulfides that are pharmaceutically important and demanded in Lee and Song and co-workers proposed a convenient
material chemistry to be efficiently obtained (Scheme 84, D). method for the preparation of benzothiazoles via a three-
The known reaction for the preparation of diaryl sulfides by component reaction of ortho-iodoaniline with aldehyde and
using Na2S105,404 was carried out under milder conditions than NaSH·nH2O (Scheme 86, B).411 However, in the case of R2 =
previously described, with a high yield (Scheme 85, A).405 The p-ClC6H4 or iPr, the reaction did not proceed. A large series of
synthesis of Ph2Se by using elemental Se also proceeded with a compounds with substituents in aromatic rings were obtained.
high 96% yield (94% isolated). Of note, in 2009, Ma, Jiang, and co-workers obtained 2-
Zhang and co-workers synthesized benzo[b]thiophene in substituted benzothiazoles in a two-component reaction using
moderate to good yields via the Cu(I)-catalyzed reaction of 2-haloanilides and Na2S·9H2O as starting compounds.105
ortho-bromoalkynylbenzenes with Na2S as a sulfur donor In 2010, Li and Zhang and co-workers proposed the
(Scheme 85, B).406 This reaction can also proceed without a preparation of 2-CF3-substituted benzothiophenes and benzo-
catalyst at high temperature (NMP, 180 °C). thiazoles via a CuI-catalyzed thiolation−annelation reaction
The preparation of 2,3-dihydrothiophenes followed by with Na2S or NaSH (Scheme 86, C).412 The products were
oxidation to di- and trisubstituted thiophenes is achieved by obtained in moderate to high yields.
S-alkylation and S-alkenylation of 1,4-diiodobut-1-enes and Diaryltrithiocarbonates were synthesized via the CuI-
Na2S in a sealed tube (Scheme 85, C).407 F. catalyzed three-component reaction of ArX with Na2S and
Formation of the C(sp2)−SH bond and annelation upon the carbon disulfide (Scheme 86, D).413 ArI is efficient in the
preparation of 2-substituted benzothiophenes was studied reactions with both electron-withdrawing and electron-
using NaSH and Cu(OTf)2 catalysis (Scheme 85, D).408 The donating substituents, while ArBr is efficient only with
same authors carried out a one-pot process with the electron-withdrawing substituents: the product is produced
participation of NaSH, including cross-coupling/attachment in a lower yield (60−70%) at a higher temperature (130 °C)
at the triple bond (6-exo-dig cyclization). The product was and a longer reaction time.
produced in good to high yields. Notably, CuI catalyzed both Diaryl sulfides, as well as sulfide-containing cyclic com-
stages (Scheme 85, E).409 pounds, could be prepared using CS2 alone as a sulfur source.
The synthesis of 2-aminobenzothiazoles from carbodiimide After optimization, a large series of compounds were obtained
and sodium hydrosulfide and from N-(2-iodophenyl) triphe- in good yields (Scheme 87, A).414 Similar conditions were used
Chem. Rev. 2022, 122, 16110−16293
Scheme 84
to obtain cyclic sulfides (Scheme 87, A). The role of DBU is to of ortho-iodoanilines with CS2 and thiols under CuBr catalysis
form HS and CuSH, as well as to deprotonate ArSH (Scheme (Scheme 88, B).
87, B). Thiourea is a convenient source of sulfur. Symmetric diaryl
The CuI-catalyzed formation of symmetric and unsymmetric sulfides were obtained in good yields via the reaction of aryl
diarylsulfides with the participation of CS2 and amine in the halides with thiourea under CuI/DMAP (4-(dimethylamino)-
presence of KOH was described.415 Substituted 2-amino- pyridine) catalysis (Scheme 89, A).418 The authors emphasized
benzothiazoles were prepared by Ma and co-workers416 via the the simplicity and cost-effectiveness of the proposed method.
S-arylation/heterocyclization domino reaction (Scheme 88, A). CuSO4·5H2O-catalyzed arylation of thiourea by aryl iodide
Ma and co-workers417 also proposed the synthesis of 2-thio- in water produces S-arylisothiourea in good to excellent yields;
substituted benzothiazoles via the domino reaction: con- that is, it stops at the first stage of sulfide formation (Scheme
densation/S-arylation/heterocyclization upon the interaction 89, B).419
Chem. Rev. 2022, 122, 16110−16293
Scheme 85
The reaction with p-nitroiodobenzene proceeded with a low Along with thiourea, thioacetamide can serve as a good
yield (33%), and low yields were also obtained upon arylation source of sulfur and, judging by ref 425, can be more efficient
of m-I-, o-Br-, and o-Cl-phenyl-substituted ureas (61%, 50%, in the reaction with aryl halides. It was used to obtain a large
and 45%, respectively). The obtained compounds can be series of diaryl sulfides under catalysis by Cu(I) without a
subsequently transformed into biologically active compounds. ligand with aryl iodides and bromides (Scheme 92, C).
A three-component reaction involving phenol esters and Zhou and co-workers used reactions with ArI and ArBr with
alkyl halides is catalyzed by CuI in wet PEG-200 to produce KSCN to prepare diaryl sulfides (Scheme 93, A).426 Later, it
arylalkyl sulfides in good (>80%) to high (90%) yields was shown that the reaction proceeded well in PEG-400.427 It
(Scheme 90).420 Of note, PEG in this case plays the roles of is assumed that the hydrolysis of PhSCN leads to the
both solvent and ligand. formation of PhS−.
Arylthiopyrimidines are formed from 3,4-dihydropyrimidine- A similar reaction was carried out under catalysis by Cu2O
2(1H)-thiones in the CuI-catalyzed Ullmann-type process and microwave irradiation (Scheme 93, B).428 The reaction did
(Scheme 91 (1)).421 The transformation of 3,4-dihydropyr-
not proceed with 3-iodopyridine, while with aryl bromides, the
imidine-2(1H)-thiones via tautomeric transformation, Ullmann
yields were decreased significantly. This reaction has been
coupling, oxidation, and elimination−aromatization leads to
the formation of arylthiopyrimidines (Scheme 91 (2)).422 demonstrated earlier for selenium (Scheme 93, C (1)).429 A
Aminourea is a good surrogate for sulfur upon Cu(OAc)2 possible mechanism includes cross-coupling, hydrolysis of the
catalysis in DMSO without ligand (Scheme 92, A).423 Using cyanide being formed, and subsequent selenylation (Scheme
dithiooxamide as a sulfur surrogate in the CuI-catalyzed 93, C (2)).
reaction with PhI required significant optimization since it A direct synthesis of benzisothiazol-3(2H)-one was carried
produced a mixture of diaryl sulfide and diaryl disulfide. Only out by using not only sulfur powder but also KSCN.430
the usage of CuI−K2CO3−PEG-200 reduced the formation of Interestingly, the reaction was carried out in water with the
disulfides to trace levels (Scheme 92, B).424 High yields were same catalyst in the presence of DABCO and Bu4NI. The
observed for ArI with electron-donating substituents, and the yields were rather moderate, and the temperature used was
yields decreased dramatically upon introducing electron- higher than that in ref 384 (Scheme 94, A).
withdrawing groups into the benzene ring (in the case of p- Sucheck and co-workers presented an interesting study of
NO2 substituent, 55% for ArI and 52% for ArBr). C−Se bond formation in the synthesis of 2-alkyl-1,2-
Chem. Rev. 2022, 122, 16110−16293
Scheme 86
Scheme 87
Chem. Rev. 2022, 122, 16110−16293
Scheme 88
Scheme 89
Scheme 90
benzisoselenazol-3(2H)-ones catalyzed by Cu(I) under termi- performed a CuONP-catalyzed one-pot reaction of 1,3-dienyl
nal and photoinduced activation (Scheme 94, B).431 bromides and1,3-dienyl-gem-dibromides with KSeCN (Scheme
Under thermal action, 14 compounds were obtained with 96).432 The reaction mechanism is still being studied, but it
yields from 23% to 91%. Under photochemical exposure (UV can be assumed that cross-coupling followed by cyclization
light 250−360 nm), the reaction still required CuI but did not occurs.
need a ligand, and the yield reached 92%. Although the results 2-Iminobenzo-1,3-oxathioles were obtained via the reaction
were similar, the mechanisms probably differed: atom transfer of ortho-iodophenol with isothiocyanates catalyzed by CuCl2/
for the thermal reaction and SET for photoinduction. 1,10-phen in H2O in the presence of DABCO (Scheme 97,
On the basis of 2-(4-azidophenyl)benzo[d][1,2]selenazol3- A).433 Synthesis of 2-aminobenzothiazole via the reaction of
(2H)-one, a compound with antituberculosis activity was isothiocyanate with 2-iodoaniline with 50 ppm of CuI was
synthesized (Scheme 95). carried out (Scheme 97, B).434 A convenient method for the
An interesting protocol for the production of selenophenes synthesis of 2-aminobenzothiazoles435 and 2-aminobenzosele-
and thiophenes was proposed by Ranu and co-workers, who nazoles436 is the Cu-catalyzed reaction of 2-iodoanilines with
Chem. Rev. 2022, 122, 16110−16293
Scheme 91 To prepare thioesters, the authors440 used stable and easily

obtainable sulfonyl hydrazides (Scheme 100). It was shown
that this reagent in the presence of DBU/AcOH became a
source of the HS group.
Thiocarboxylic acids were used as a sulfur source in the
CuI/phen-catalyzed cross-coupling reactions with (2-
iodophenylimino)triphenylphosphorane or (2-iodobenzyl)-
triphenyl-phosphonium bromide. The reaction involved
cross-coupling followed by cyclization, and it could serve as
a practical method for the preparation of benzothiazoles
(Scheme 101).441
The tandem reaction for producing aryl-substituted
benzothiazoles, described by Liang and co-workers, involves
Ullmann coupling and intramolecular heterocyclization at the
isothiocyanates435 or isoselenocyanates436 (Scheme 97, C). C(sp3)−H bond. Upon the participation of K2S in the reaction
The reaction proceeds via the stages of hydroamination and Se with N-benzyl-2-iodoaniline, a large series of substituted
cross-coupling with the formation of a Cu(III) intermediate benzothiazoles were obtained (Scheme 102 (1)).442 The
(C). following reaction mechanism was proposed (Scheme 102
A convenient method was proposed for the synthesis of (2)).
benzo[4,5]thiazolo[2,3-c][1,2,4]triazoles in the one-pot reac- Liang and co-workers443 used K2S to produce isoquinoline-
tion of o-bromo-arylisothiocyanates with aroylhydrazides. In fused 1,3-benzothiazines (pharmacological compounds). This
this reaction, at the first stage, the C−N bond is formed, and at synthesis involved the formation of a C(sp2)−S bond and
the second stage, the C−S bond is formed intramolecularly, subsequent oxidative cyclization with functionalization of the
and a tricyclic system arises. The reaction is catalyzed by
C(sp3)−H bond. This is another example of a Cu-catalyzed,
Cu(II) in water (Scheme 98, A).437
one-pot, two-step synthesis of complex organic compounds
The CuCl2-catalyzed cascade reaction of o-bromoaryl
isothiocyanates with isocyanides produces benzo[d]imidazo- (Scheme 103, A).
[5,1-b]thiazole (Scheme 98, B).438 Pyridine derivatives were Benzothiazolones were obtained upon the action of K2S on
formed in high yields. The mechanism of the reaction was ortho-iodoanilines in DMF (Scheme 103, B (1)).444 The
proposed to include the formation of Cu(IV) at the S-cross- reaction product is supposedly formed according to the
coupling stage (Scheme 98, B). following reactions (Scheme 103, B (2)). The synthesis of
Patel and co-workers carried out copper-catalyzed produc- benzo[b]thiophene/imidazo[1,2-a]pyridines containing two
tion of aryltylbenzothiazole via a two-step reaction, which pharmacophore fragments (benzothiophene and imidazopyr-
included intra- and intermolecular thiolation. A study of seven idine) was carried out in a one-pot process with the
nitrogen-containing ligands showed that the less expensive 1,2- participation of K2S under CuI catalysis as a result of cross-
diaminocyclohexane produced the best results (Scheme 99).439 coupling and intramolecular thiolation (Scheme 103, C).445
Scheme 92
Chem. Rev. 2022, 122, 16110−16293
Scheme 93
Scheme 94
Scheme 95
This reaction was simultaneously described in ref 446 but at participation of molecular sulfur or potassium sulfide under
a higher temperature. The reaction was applied to the synthesis CuI/I2 catalysis (Scheme 103, D).
of benzothiophene-fused indoles. The synthesis was carried out A three-component reaction of ortho-iodoanilines with
with the formation of two C(sp2)−S bonds upon the potassium sulfide and isocyanide produced benzothiazole-
Chem. Rev. 2022, 122, 16110−16293
Scheme 96
Scheme 97
thiones in good to high yields (Scheme 104, A).447 The Reeves and co-workers described the formation of C−S
proposed reaction mechanism did not consider the change in bonds via the reaction of Bunte salts (RS−SO2ONa) with the
the oxidation state of copper (Scheme 104, B). Grignard reagent. The salts themselves (R = Ar, vinyl) were
The CuI/DMAP-catalyzed reaction with sodium thiosulfate obtained from ArX by the CuI·DMEDA-catalyzed reaction
proceeds with high yields (Scheme 105, A).448 In a three- with Na2S2O3 in high yield.452
component reaction of ortho-iodaryl triazenes, benzyl chloride, As in the series of reactions catalyzed by Pd, in the reactions
and Na2S2O3 as a sulfurating reagent, arylbenzyl sulfides were catalyzed by copper, DMSO can act as a donor of the CH3S
obtained in moderate to high yields. The successful reaction group,106 which is converted to the sulfonyl group by aerobic
required a promoter, and BF3·OEt2 demonstrated the best oxidation. Cu2O/KOtBu catalysis afforded a large series of
results (Scheme 105, B).449 The authors suggested a radical arylmethyl sulfones in moderate to high yields (Scheme 107
mechanism of the reaction. (1)). Methylthiolation of aryl iodides with different functional
The reaction of 2-aminobenzothiazole with aryl iodides in groups was carried out under the action of dimethyl sulfoxide
the presence of a copper catalyst and KOtBu proceeded with mediated by CuBr/ZnF2 (Scheme 107 (2)).453
ring opening and the formation of 2-(arylthio)arylcyanamide A similar reaction is described in ref 454 where it was shown
(Scheme 106, A).450 In a similar way, unsymmetrical diaryl that Zn(OAc)2 can be used instead of ZnF2.
sulfides are obtained by Cu(I)-catalyzed ring opening of Under CuCl catalysis, 2′-cyanoethyl thioglycoside forms a
benzothiazole under the action of a base in water (Scheme thioglycoside anion, which is subsequently arylated or
106, B).451 heteroarylated to form sulfide (Scheme 108).455
Chem. Rev. 2022, 122, 16110−16293
Scheme 98
Scheme 99
Scheme 100 A large series of biologically active compounds were

obtained. An example of a C−S glycosidic bond in natural
compounds can be found in the antibiotic Lincomycin A.456
An interesting source of sulfur is Lawesson’s reagent
[ArP(S)S−]2, with which sulfides are formed in the reaction
of ArHal with primary and secondary alcohols catalyzed by
CuI in diglyme.457
The authors458 proposed a method for the preparation of
symmetric diaryl and dialkyl disulfides from aryl and alkyl
halides using potassium 5-methyl-1,3,4-oxadiazole-2-thiolate as
a source of S and simultaneously a base and ligand for copper
(Scheme 109).
Chem. Rev. 2022, 122, 16110−16293
Scheme 101
Scheme 102
Cross-coupling of ArX/B(OH)2 with sulfonic acid salts, The reaction does not proceed with chlorobenzene itself and
catalyzed by Cu, leads to the production of various its para-acyl derivatives.465
arylsulfones, as shown in Scheme 110, A.459,460 Of note, However, to obtain the sulfone ArSO2CF3, which could have
these reactions were first carried out by Wang and Baskin interesting medicinal properties, a stronger arylating agent was
under Cu(OTf)2/DMEDA catalysis461 and Ma and Zhu under required. Shekhar and co-workers demonstrated that sodium
CuI/L-proline catalysis.462 trifluoromethanesulfinate reacted with the diaryliodonium salt
The reaction of aryl iodides and bromides with sodium under Cu2O catalysis and produced aryl trifluoromethyl
aryl(alkyl)sulfinate catalyzed by CuI with D-glucosamine as the sulfones in good to high yields (Scheme 113).466 The reaction
green ligand produces diaryl and arylalkyl sulfones in a DMSO· of (2-thienyl)2 IOTs proceeded with a 66% yield.
H2O mixture (Scheme 110, B).463 Recyclization of the catalyst Upon CuI-catalyzed interaction of sodium p-toluenesulfinate
is possible with a “fresh start” methodology. The reaction is with arenediazonium salts, sulfones are produced in good
readily scalable (Scheme 110, C (1)). The methodology was yields (Scheme 114, (1)).101 The resulting copper salt
used in the synthesis of the drug zolimidine (Scheme 110, C ArSO2Cu supposedly reacts with ArI to form the Cu(III)
(2)). complex (Scheme 114, (2)).
However, the reaction of aryl iodides with sodium A convenient method for the preparation of diaryl(dialkyl)-
arylsulfinate can produce sulfides, for example, under CuO/ disulfides via the reaction of RX with thioacetamide was
DABCO catalysis (Scheme 111).92 proposed (Scheme 115).467 However, it should be noted that
In this reaction, DABCO and its concentration play a special the same authors showed that various thiols were oxidized by
role in the formation of RSO2•. The authors suggest a radical Cu(II) in EtOH/H2O, producing disulfides in high yields.468
pathway with the formation of a DABCO-N-oxide radical 1,3-Benzoxazole-2-thiol was proposed to be used as a
cation. surrogate in the FeCl3/CuO-catalyzed synthesis of symmetric
The heterogeneous Cu(OAc)2 catalyst on chitosan showed and asymmetric thioesters. The reaction proceeded via the
excellent results in the reaction of ArX with RSO2Na. The formation of arylated 2-(arylsulfenyl)-1,3-benzoxazole, which
catalyst is obtained easily, and its activity remains almost the underwent a second arylation with displacement of the
same in five cycles (Scheme 112, (1)).464 The reaction is used benzoxazole nucleus without isolation (Scheme 116).469
in a one-pot synthesis of zolimidine (antiulcer) (Scheme 112, Previously, these authors showed that a bimetallic iron−
(2)). copper catalyst allowed the introduction of alkyl-, aryl-, and
Under microwave irradiation, the CuI-catalyzed reaction of heteroarylthiols into 6-iodoimidazo[1,2-a]pyridine.470
aryl chlorides with EWG and aryl- (heteroeryl, cyclopropyl) 4.2.1.3. Heterogeneous Copper Catalysis in Ullmann-Type
sulfinate sodium was carried out. In a short time (3−30 min), Processes. Heterogeneous catalysis, which allows easy
asymmetric sulfones (39 examples) were formed in high yields. separation of the catalyst from the product and regeneration
Chem. Rev. 2022, 122, 16110−16293
Scheme 103
and reuse of it, sometimes repeatedly, is naturally attractive good (sometimes close to quantitative) product yields. The
from the viewpoints of both economy and environmental copper catalysts included not only powders of copper471 but
safety. In modern Ullmann chemistry, it began to be used also its salts472−474 and oxides,475−478 and these oxides
almost simultaneously with the beginning of the development
contained both Cu(I) and Cu(II).
of this direction, and the beginning of the 21st century was
marked by the appearance of a large number of works, in which Some of these reactions were carried out in water,477,479,480
cross-coupling of aryl halides with aromatic and aliphatic thiols both with481 and without ligands,474,476,482 and were equally
was carried out under various heterogeneous conditions with successful.
Chem. Rev. 2022, 122, 16110−16293
Scheme 104
Scheme 105
Scheme 106
We have already mentioned later works when discussing the the mechanism, in which Cu(I)/Cu(II) or radical processes
“Modern Ullmann” realized with various sources of sulfur. involving Cu(0) are included.
Here, we will supplement this most important type of reaction The use of nanoparticles in catalysis turned out to be
with other examples, especially those related to nanocatalysis, extremely fruitful in all respects.49,483 Due to their high surface
although it should be noted first that the mechanism of such area, exceptional thermal stability, easy separation from the
heterogeneous reactions is still not clear. Typical pictures of reaction mixture, and recyclability, they have immediately
the catalytic cycles, as shown in Figure 27, are consistent with attracted the attention of not only catalytic chemists but also
Chem. Rev. 2022, 122, 16110−16293
Scheme 107
Scheme 108
Scheme 109 The same copper complex grafted onto mesoporous SBA-15
catalyzed a three-component reaction of aryl halides with
thiourea and benzyl bromide (Scheme 118).487
Successful reactions of thiolation of aryl bromides with
thiophenol, catalyzed by the Cu-grafted furfural-imine-
functionalized nanocatalyst Cu−F−MCM-41 under aerobic
conditions (10 examples, 75−88%) and a three-component
reaction with thiourea in the presence of benzyl bromide,
catalyzed by copper on mesoporous SBA-15 in an aqueous
medium, were described. Both catalysts could be recycled with
synthetic chemists. The economic and environmental benefits a gradual decrease in the product yield.488
A three-component reaction of aryl halide with thiourea and
are evident.
benzyl bromide was studied under catalysis by CuNPs on 2-
Notably, the rapidly developing direction of nanocatalysis
methoxy-1-phenylethanone-modified MCM-41 (Scheme
has already shown outstanding results in the reactions of
119).489
C(sp2)−S bond synthesis. Although we still cannot explain
Under the corresponding conditions (H2O, KOH, 10−12 h,
why the CuONP-catalyzed reaction of ArHal with PhSH 100 °C), the products (14 examples) were obtained in 74−
proceeds at room temperature,484 why the reactions do not 88% yields. The catalyst turned out to be active in an aqueous
require a ligand,485 and how not only activated ArCl479 but medium and recyclable�the yield dropped insignificantly (79
also unactivated ArHal can possibly be involved in the reaction. → 74%) in five cycles, although the reaction completion time
The role of radical processes in the application of nanocatalysis increased from 10 to 12 h.
has not been clarified either. Hajipour and co-workers proposed a new efficient and
Let us start the discussion with heterogenized catalysts, in recyclable heterogeneous nanocatalyst, Cu(II)NPs, on histi-
which copper complexes, being bound to a support via a dine-functionalized chitosan. The catalyst was tested on two
special linker, exhibit the properties of heterogeneous catalysts. reactions: the above-shown three-component reaction of aryl
The reaction from ref 486 can serve as an example, in which a halides with thiourea and benzyl bromide (in water, 100 °C,
copper−Schiff base complex is bound to polystyrene via a 10−12 h, 12 examples, 75−86%, R = H, X = Br (80%); R = H,
linker (Scheme 117). The catalyst was recycled with a X = Cl (76%)) and a two-component reaction of aryl halides
noticeable decrease in the activity by the fifth cycle. with potassium thiocyanate (Scheme 120).490
Chem. Rev. 2022, 122, 16110−16293
Scheme 110
Scheme 111 Scheme 113
By using diphenyl sulfide as an example, recyclization was in a one-pot, three-component reaction of C−S bond
carried out: in the fifth cycle, the yield dropped from 90 to formation (Figure 28). Arylbenzyl sulfides (14 examples)
80%, and the time increased from 24 to 26 h. Notably, the size were obtained in 70−79% yields when using aryl bromides and
(7.5 nm) and morphology of the catalyst did not change. aryl chlorides.492
The same authors proposed another catalyst (Cu(II)-Et-S@ The catalyst was recycled (six cycles) with a minimal loss in
MCM-41) for a trimolecular reaction.491 Arylbenzyl sulfides the product yield (79 → 74%).
(13 examples) were obtained in 70−85% yields (Scheme 121). The reaction between aryl halides and potassium thiocya-
The catalyst was recycled in five cycles with a small yield nate, catalyzed by a copper complex linked to polystyrene and
decrease (75 → 72% in 10 h). resulting in the formation of symmetric diaryl sulfides,
The Cu-PIF-SBA-15 catalyst obtained by immobilization of proceeded in water with good to high yields. In five cycles,
copper on SBA-15 and modified via the reaction of the amino there was a slight decrease in the yield (95 → 93%) (Scheme
group with phloroglucinol-dialdehyde showed excellent results 122, A).493
Scheme 112
Chem. Rev. 2022, 122, 16110−16293
Scheme 114
Scheme 115
Zhao and Cai and co-workers synthesized the C(sp2)−S

bond via the reaction of aryl halides with potassium
thiocyanate in neat water catalyzed by CuCl immobilized on
MCM-41 containing ethylenediamine in the linker (Scheme
122, B).494 In ten successive cycles, the yield changed
insignificantly (88−85%). However, aryl bromides did not Figure 27. Representation of Cu-nanocatalyzed S-cross-coupling.
react under these conditions.
The reaction of aryl halides (X = I, Br) with xanthogenate in Scheme 117
water, catalyzed by CuNPs on polyaniline supported on
multiwall carbon monotubes, carried out in the presence of
aryl, benzyl, and alkyl halides, was also successful, producing
asymmetric sulfides (Scheme 123). Recyclization (six cycles)
proceeded with practically no decrease in the product yield (95
→ 93%).495
The complex Cu(II)-grafted furfural-functionalized meso-
porous organosilica allowed us to obtain thioethers in good
yields and to reuse the catalyst repeatedly. The catalyst was
recycled in five cycles with a slight yield decrease (Scheme 124,
A).496
CuI-cryptand 22 on polystyrene resin was a highly efficient
and recyclable catalyst for the formation of C(sp2)−S bonds in
aqueous media (Scheme 124, B).497 Five cycles were carried
Scheme 116
Chem. Rev. 2022, 122, 16110−16293
Scheme 118
Scheme 119
Scheme 121
Scheme 123
thiosemicarbazide) leads to symmetric sulfides in a reaction

with elemental sulfur and solventless urea (Scheme 125).498
The catalyst was recycled seven times, with a slight decrease in
the product yield.
The use of copper on iron supports, which allows the use of
an external magnet to remove the catalyst from the reaction
mixture, seems very attractive.
A heterogenized copper complex (FMNPs@SiO2-Tpy-Cu)
proved to be an efficient and recyclable catalyst for Ullmann
coupling (Scheme 126, A).499 The reaction did not proceed in
the case of PhCl with PhSH and nBuSH with PhI.
A magnetic nanoligand in the presence of CuI produces a
Figure 28. Structure of complex Cu-PIF-SBA-15. catalyst that allows obtaining a C(sp2)−S bond in the reaction
of heterocyclic thiols with aryl iodides in good to excellent
out in the reaction of iodobenzene with thiophenol with a yields (Scheme 126, B). The catalyst was recycled five times
gradual yield decrease (from 96% to 88%). with little loss of activity (94% → 89%).500
A heterogenized copper complex (SBA-16/GPTMS-TSC- A particularly interesting area of catalysis is catalysis by
Cu(I), GPTMS = 3-glycidyloxypropyltrimethoxysilane, TSC = copper deposited directly onto hard or soft supports.
Chem. Rev. 2022, 122, 16110−16293
Scheme 124 Baig and Varma studied the reaction of aromatic thiols with
aryl iodides and bromides catalyzed by nanoparticles of copper
on a magnetic carrier (iron ferrite, dopamine-doped) under
MW irradiation (Scheme 127).501
Scheme 127
In a model reaction, recyclization was carried out: three

cycles proceeded without a noticeable change in the activity
and without a change in the copper content in the catalyst.
A bimetallic system based on copper on iron catalyzed the
reactions of aryl iodides with thiols in DMAA at 100 °C in high
yields. Due to the ability of iron to exhibit reducing properties,
the formation of the byproduct diaryldisulfide at the initial
stage of the reaction was minimized. The catalyst was recycled
five times with a slight drop in the yield by the fifth cycle (from
98 to 80%) (Scheme 128, A).502 Aryl bromides and aryl
chlorides with electron-withdrawing groups react with
thiophenols for a longer time.
Scheme 126
A similar reaction of aryl halides with thiophenols was
carried out using mesoporous Cu−Fe derived from hydro-
talcite without a ligand as a catalyst (Scheme 128, B).503 The
catalyst was recycled five times without a loss of activity.
Sharma, Gawande, and co-workers485 used a maghemite (γ-
Fe2O3)-supported nanocomposite (20−40 nm, 80% Cu(0),
20% C(II)). Recycling proceeded with a decrease in the
product yield from 94% to 88% at the sixth cycle.
Nageswar and co-workers 504 performed arylation of
aromatic and aliphatic thiols and diphenyl disulfide catalyzed
by CuFe2O4 nanopowder in DMSO in the absence of a ligand
under an inert atmosphere. The catalyst was recycled four
times without changing the catalytic activity.
The same group arylated diselenides under the same
conditions505 with Ph2Se2 as a selenium source using copper
ferrite nanoparticles. The reaction with iodides (Ar, Het, Alk)
proceeded with high yields (70−98%); however, with aryl
bromides, the yields dropped to 60−78%, and aryl chlorides
did not react. Recycling proceeded with a gradual drop in the
product yield from 98% to 89% in the third cycle.
Catalysis by copper on a magnetic support provided high
yields of diaryl sulfides in the reaction of thiophenol with aryl
Chem. Rev. 2022, 122, 16110−16293
iodides with neutral and electron-withdrawing substituents;

with ArBr and ArCl, the yields were good and moderate,
respectively (Scheme 129).98
Scheme 129
HetSH and AlkSH reacted with PhI with good yields.
Recyclization of the catalyst (5 cycles) proceeded with a

slight decrease in the yield (95 → 90%). Moreover, the authors
found a weak leakage of copper and iron into the solution.
Considering the known drugs with a dibenzothiazepine
fragment, the authors demonstrated the applicability of their
method to the synthesis of this fragment.
The heterogeneous catalyst CuFe2O4 NP506 in the absence
of ligands in water catalyzes the reaction of E- and Z-styryl
halides with electron-donating and sterically overloaded
arylthiols, producing the corresponding sulfides with high The heterogeneous version of the Ullmann-type process
yields and stereoselectivity (Scheme 130). with the participation of thiourea produced high yields in the
Sterically hindered diaryl sulfides (four examples) and bis- reaction with aryl iodides (75−97%) and good yields with aryl
sulfides (four examples) are also obtained with good yields. bromides (59−73%) (Scheme 131, A).507 The catalyst was
The catalyst was used in ten successive cycles, and the yield recycled with a drop in the yield.
loss was relatively low. The reaction of aryl halides, including aryl chlorides, with
thiourea catalyzed by nano-CuFe2O4 without a ligand was
Scheme 130
Chem. Rev. 2022, 122, 16110−16293
Scheme 131
described. The catalyst was used in six cycles (94 → 90%) Cu(0)NPs immobilized on SBA-15 silica modified with (3-
(Scheme 131, B).508 A CuFe2O4-catalyzed three-component aminopropyl)thienoxysilane for catalyzing the thiolation of aryl
reaction involving various sulfur donors was carried out by and styryl halides with high yields (especially for iodides) and
Gholinejad and co-workers509,510 to obtain trithiocarbonates good TON and TOF values without any ligand or solvent.515
(a) and thioethers in a “green” solvent (b) (Scheme 131, C). The catalyst was recycled (5 cycles) with a minimal loss in the
Of note, iron itself can also catalyze reactions. The product yield (Scheme 132, B).
authors511 showed that Fe3O4 stabilized by mesoporous Routing and co-workers have recently obtained remarkable
polyaniline (PANI) catalyzed the reactions of aryl chlorides results when studying an S-cross-coupling reaction under
with thiophenols and aryl iodides with thiourea in water with cooperative catalysis. CuMoO4 nanoparticles obtained via the
the formation of sulfides. At that time, the catalyst did not lose reaction of CuCl2 with (NH4)6Mo7O24.4 and doped with
activity in five successive cycles (Scheme 131, D). Mo(VI) were able to catalyze the formation of C(sp2)−S
Nanocoppers on modified 2-methoxy-1-phenylethanone
bonds at room temperature for various aryl halides (including
(MPE) zeolite (Cu(II)-2-MPE@MCM-41, MCM = mobile
ArF). These NPs were active not only for aryl thiols but also
composition of matter #41, mesoporous material) catalyze the
reaction of aryl halides with urea. Aryl bromides and aryl for alkylthiols when using CuMoO4−DMSO−Cs2CO3. The
chlorides react surprisingly well. The catalyst was recycled six catalyst was recyclable (Scheme 133).516
times with a gradual decrease in activity (82% to 75%) According to the proposed reaction mechanism, oxidative
(Scheme 131, E).512 addition to the bimetallic catalyst took place followed by an
High catalytic activity in the reactions of arylthiols with aryl exchange of X for RS (Figure 29).
iodides was demonstrated by copper nanoparticles (60% A new recyclable catalyst Cu(I)-USY (ultrastable Y zeolite)
Cu(0) and 40% Cu(I) with Cu(II) (2−3 nm)) immobilized was used for the synthesis of unsymmetrical sulfides (Scheme
on silicon oxide under MW irradiation.513 134, A).517 Silica-supported nanocoppers proved to be efficient
CuNPs immobilized on zeolite (Na−Y) proved to be an in the reactions of aryl iodides and aryl bromides with aliphatic
excellent catalyst for the reaction of arylhalides with thiols. The and aromatic thiols.518 The catalyst was recycled three times,
catalyst was recycled four times without a loss of activity and the yield product decreased by the third cycle (Scheme
(Scheme 132, A).514 Excellent results were described using 134, B).
Chem. Rev. 2022, 122, 16110−16293
Scheme 132
Scheme 133
Copper nanoparticles on chitosan were efficient in the PhI the reaction proceeded with an excellent yield (99%) and
reactions of aryl iodides with thiophenol in toluene. 4- with PhBr in a good yield (82%), and even with PhCl a
Nitroromobenzene and 4-nitrochlorobenzene reacted with moderate yield (56%) was observed. A catalytic cycle with the
thiophenol in lower yields. The catalyst was recycled four participation of Cu(0) → Cu(II), identical with the one shown
times, with a noticeable drop in the product yield after the first above, was proposed.
cycle (Scheme 134, C).519 The reaction of aryl iodides with diaryl disulfides catalyzed
CuNPs on amine-doped mesoporous zirconia exhibited high by CuNPs in PEG400 in the presence of KOH allowed the
activity (Scheme 134, D).520 The authors showed that with preparation of unsymmetrical diaryl sulfides in good to high
Chem. Rev. 2022, 122, 16110−16293
Scheme 134
Scheme 135
Chem. Rev. 2022, 122, 16110−16293
yields. In four successive cycles, the yield dropped from 95% to DMSO, 110 °C, 21 h).292 The synthesis of 4,7-bisarylsulfenyl-
85% (Scheme 134, E).521 and 4,7-bis(arylselanyl)benzo[c]-[1,2,5]thiadiazole, which
Ranu and co-workers carried out a CuNP-catalyzed three- were of interest due to their electro-optical properties, was
component reaction of aryl iodides or styryl bromides with carried out (Scheme 136, C).526
carbon disulfide in water. The catalyst was recycled four times Reactions of PhI with phenyl- and p-tolylthiols were carried
with no noticeable loss of activity (Scheme 135, A).522 Of out using a heterogeneous catalyst (CuO)x/mesoporous
note, vinyl bromides react with high stereoselectivity. A nitrogen-doped carbon material (meso-N-C-1) in DMSO
catalytic cycle with the participation of Cu(0) and Cu(II) with KOH at 100 °C. The reactions proceeded with yields
was proposed (Figure 30). close to quantitative (98% and 96%, respectively). Recycliza-
tion (5 cycles) was carried out without a loss of the product
yield.527
The authors528 obtained CuO hollow nanospheres by
controlled oxidation of nanocubic CuOs and compared their
activity with nanoparticles deposited on acetylene black
(CuO/AB) and charcoal (CuO/C) in the Ullmann coupling
combination of aryl iodides and thiols. Under comparable
conditions, CuO/AB showed the best activity and selectivity
toward disulfide (Scheme 136, D). However, in the case of
acceptor substituents, a mixture of mono- and disulfide is
formed, and with strong donor substituents, only a disulfide is
formed.
Another example of an efficient and recyclable catalyst is
given in ref 529 for a three-component reaction (Scheme 136,
E).
Figure 29. Catalytic cycle for CuMoO4-catalyzed S-cross-coupling. Nano-CuO on graphene oxide turned out to be a very
efficient catalyst in the synthesis of symmetric and asymmetric
arylsulfides.530 With aryl iodides, the reaction proceeded with
high yield and selectivity without a ligand and solvent in the
presence of a weak base for both aromatic and aliphatic thiols.
Surprisingly, the reaction of ArCl in DMSO also proceeded
with a good yield, although it depended on the thiol. Thus,
with cyclohexylthiol, the yield dropped to 55%. In these
reactions, a disulfide was also formed (up to 10% for
thiophenol and 15% for CySH). Six recycles proceeded with
a small loss in the product yield. Thiolation of ArI with aryl
and alkyl thiols was catalyzed by Cu2O (KOH, 1,4-dioxane)
(Scheme 136, F).478
Spherical CuO particles (40−70 nm) react with aryl iodides
(60−97% in 4.5−9 h), aryl bromides (73−87% in 12.5−15 h),
and even aryl chlorides (DMSO, Cs2CO3, 50−86% in 14−24
Figure 30. Catalytic cycle for the copper-catalyzed reaction of aryl h) in the presence of Et3N without a solvent at 90 °C but with
iodides with amine and CS2. a high yield of the byproduct diaryldisulfide (up to 20%). The
catalyst was recycled up to six times without a loss of the
Nanosized CuI particles demonstrate high efficiency in the product yield. However, with KOH, it could be recycled only
S-arylation reaction in water.474 In the reaction of iodobenzene four times, with a noticeable drop in the yield. Thus, the
with thiophenol in the CuI−nano-nBu4NOH−water system at impact of the base on both the deprotonation of thiol and the
50 °C, the product yield (isolated) was 93% (Scheme 135, B). state of the catalyst was noted.
Reactions of ArI with aromatic (24 examples) and aliphatic (20 CuONP-catalyzed reactions of ArX with (PhSe)2 proceeded
examples) thiols, as well as reactions of ArBr (28 examples, 80 very well with the formation of mixed diaryl selenides.531
°C, 48 h), demonstrated excellent results. The catalyst was CuONPs were used to prepare diaryl disulfides, diselenides,
recycled with a slight decrease in the yield at the fourth cycle. and ditellurides from ArX and elemental chalcogen (Y) under
It is still unclear what happens to CuO or Cu2O and to film- microwave irradiation (Scheme 137, A).532 With alkyl iodides,
covered metallic copper. All the results obtained cannot be the yield becomes moderate.
explained by leaching alone.523 However, in our pragmatic age, The same catalyst was used to synthesize alkynyl selenides
the result obtained takes priority over the theory created. and tellurides with product yields ranging from good to high.
Carrying out the reaction in an ionic liquid allows the The catalyst was recycled four times without a noticeable drop
production of diaryl sulfides in high yields and recycling of the in the yield (Scheme 137, B).533
catalyst and the ionic liquid (Scheme 136, A).524 Trivedi, Rath, Ranu and co-workers showed that, depending on the
and co-workers studied the reaction of thiophenol with aryl solvent, the reaction of RX with R2Se2 catalyzed by
iodides catalyzed by copper(II) oxide nanoparticles (Scheme heterogeneous Cu(II)/Al2O3 could proceed with iodides (in
136, B).525 A heterogeneous reaction with CuO powder water) and, with slightly lower yields, with bromides and
without a ligand produces, with some exceptions, diaryl/ chlorides in PEG-600 (Scheme 137, C). The product yield
arylalkyl sulfides in high yields (CuO (5 mol %), Cs2CO3, dropped considerably in seven successive cycles.99
Chem. Rev. 2022, 122, 16110−16293
Scheme 136
CuO in the absence of ligands catalyzes the cross-coupling well with aryl iodides and bromides (Scheme 139, A). Copper
of 4-aryl-3,4-dihydropyrimidin-2(1H)-thione with the diary- oxide NPs without a ligand efficiently catalyze the reaction of
liodonium salt, accompanied by oxidative aromatization. A aryl(heteroaryl)halides with potassium selenoisocyanate, pro-
series of 2-(thioaryl)pyrimidines, which are important bio- ducing symmetric diaryl selenides in good to excellent yields
logical and synthetic scaffolds, were obtained in good yields with iodides and in good yields with bromides (Scheme 139,
(Scheme 138, A).534 B).537
The synthesis of unsymmetrical sulfides was carried out via Using the example of m-NO2C6H4I, recyclization of the
the reaction of aryl halides with ethyl potassium xanthogenate
catalyst was carried out. The catalyst lost its activity gradually
under catalysis by CuO nano without a ligand in the presence
of another aryl halide or alkyl halide (Scheme 138, B).535 In (84% yield at cycle 1 and 80% at cycle 4), which was related to
five reaction cycles, a slight decrease in the product yield (95− its partial leaching (97%−89% catalyst recovery from the first
89%) was observed. A mechanism including the intermediate to fourth cycle).
formation of (EtO)C(S)(SAr) and its hydrolysis with the A copper complex heterogenized on MCM-41 efficiently
formation of ArSK was proposed. catalyzed the formation of symmetric diaryl sulfides in high
Nageswar536 demonstrated that the formation of symmetric yields in the reaction of aryl iodides with thioacetamide and in
sulfides under the action of potassium thiocyanate proceeded good yields in the reaction of electron-deficient aryl-
Chem. Rev. 2022, 122, 16110−16293
Scheme 137
Scheme 138
Chem. Rev. 2022, 122, 16110−16293
Scheme 139
Scheme 140
Scheme 141
(heteroaryl)bromides. Bromobenzene and p-tolyl bromoben- Application of the Chan−Lam reactions to the formation of
zene did not enter the reaction (Scheme 140).538 the C(sp2)−S bond has not been as thoroughly studied as the
In ten successive working cycles carried out with 4- reactions with the formation of the C(sp2)−N bond, but the
iodoanisole, the yield practically did not change (93−91%). examples60,61 clearly demonstrate the potential of the method
Fu and co-workers carried out the Ullmann-type process using for the formation of carbon−chalcogenide (S, Se, Te) bonds.
a base immobilized on a polymer, which allowed the reaction The classic version of such an S-arylation reaction is the
to be carried out under milder conditions (Scheme 141).539 Cu(II)-catalyzed interaction of arylboronic acids with aromatic
4.2.2. Chan−Lam Coupling Reaction with the thiols producing asymmetric diaryl sulfides. Feng and co-
Formation of the C(sp2)−S Bond. Chan−Lam coupling workers studied many examples of this reaction at room
(formerly Chan−Evans−Lam) is a coupling of arylboronic temperature using small amounts of the catalyst, environ-
acids with nucleophiles, promoted and catalyzed by copper mentally friendly EtOH as a solvent, and O2 as an oxidant
salts. This reaction was independently proposed by three
(Scheme 142, A).540 Diphenyl sulfide in gram quantities was
authors in works simultaneously published in Tetrahedron
obtained with a yield of 70%.
Letters in 1998. In this reaction with nucleophiles (Nu = N, O,
The [Cu(DMAP)4I]I complex proved to be an efficient
S, P), arylboronic acids are used instead of aryl halides. That is,
the reaction proceeds between two nucleophiles. Catalysis is catalyst in the Chan−Lam reaction (Scheme 142, B).541 A
carried out by Cu(II) salts without ligands in the presence of Cu(II) salen complex was proposed as a catalyst for the
weak bases and even without them. Due to the mild reaction of phenylboronic acid with thiophenol (Scheme 142,
conditions, the reaction turned out to be competitive with C).542
those previously described in this review.60,61 Of note, other The reaction of dichalcogenides with arylboronic acids was
organoelement compounds (Ar−Bi, Ar−Sn, Ar−Si) and other studied under catalysis by Cu(I) or Cu(II) in the presence of
metal salts as catalysts can also be used in this process. the reducing agent NaBH4. The reactivity of Ph2Y2 changed in
However, boron and copper turned out to be most suitable for the following order: Te > Se > S. Of note, the reaction
each other when interacting with H−Nu and made it possible proceeded at room temperature (Scheme 142, D).543 In the
to develop a new method for the synthesis of the C(sp2)−Nu case of diphenylditellurides and diphenyldiselenides, the
bond, especially the C(sp2)−N bond. reaction proceeded with high yields, with rare exceptions.
Chem. Rev. 2022, 122, 16110−16293
Scheme 142
Symmetrical diaryl selenides were prepared using molecular Heterogeneous versions of the Chan−Lam reaction with the
selenium. formation of the C(sp2)−S bond are still rare. Zhao and co-
S-Arylation of 2-thio-1,4-dihydroquinazolines with aryl- workers546 described the reaction of obtaining diaryl sulfides
(heteroaryl)boronic acids was carried out at room temperature under catalysis by CuSO4/1,10-phen immobilized on MCM-
without ligands but at high concentrations of a copper catalyst 41. This reaction is an example of a process in a “green
(Scheme 143, A).544 environment” (Scheme 143, C). The catalyst was used in eight
The interaction of ArB(OH)2 with mercaptobenzoic acid cycles without a change in the yield of the reaction product
was realized in water under catalysis by CuSO4/D,L-proline in (after the eighth cycle, the loss of copper was 1%).
the presence of NaOH and ethylenediamine additives. The High yields of the product in the reaction of arylboronic
idea of the work was to use nontoxic reagents only (Scheme acids with di(heteroaryl)disulfides were obtained upon using
143, B).545 Low product yields were observed for arylboronic (2-chlorobenzoyloxy)copper(I) without a ligand as a catalyst
acids with strong electron-withdrawing substituents as well as (Scheme 143, D).547 Dialkyl disulfides are inactive under these
for meta-aminophenylboronic acid (33%). conditions.
Chem. Rev. 2022, 122, 16110−16293
Scheme 143
Ranu and co-workers carried out a heterogeneous version of Tellurium and sulfur derivatives react under the same
the Chan−Lam reaction using the above-mentioned Cu- conditions, although the product yields are low for sulfur
Fe2O4NPs as a catalyst in the reaction of arylboronic acids with (Scheme 144, D (2)).
dichalcogenides (Se, Te) in PEG-400 (Scheme 144, A).548 The work by Taniguchi should be mentioned, in which the
Under similar conditions, the reaction with Ph2Se2 also reaction of various boronic acids was carried out for the entire
produced good results (19 examples, 78−92%). The oxidative triad of chalcogenes in a DMSO·H2O mixture with high yields
reaction of Ph2Y2 with CuNPs supposedly proceeds with the (Scheme 144, E).553 For AlkB(OH)2 and Alk2Y2, the yield
formation of PhY−. The catalyst was recycled eight times with drops.
a gradual decrease in the product yield. It should be noted that The use of heterogeneous catalysis by CuONPs in the
a wide variety of boronic acids (Ar, Het, , ) reaction of arylboronic acid with diaryldiselenide allowed us to
were used. In all cases, the yields ranged from good to obtain not only diaryl selenides with various substituents but
excellent. also alkylaryl selenides and even diaryl telluride in high yields
Catalysis by CuNPs on activated carbon (Cu3(BTC)2, (Scheme 144, F).554
benzene-1,3,5-tricarboxylate) produced products in good to The reaction of diaryl disulfide with arylboronic acid,
quantitative yields in the reaction of boronic acids (aryl, catalyzed by CuCl·R3P/bpy (R = Ph, Bu), leads to the
alkenyl) with diaryl- and dibenzyldiselenides (61−100%).549
formation of a mixed sulfide and an ortho-hydroxylation
Cu(II) immobilized on the porous covalent imine network
product, for which the disulfide is a directing group. This
material (CIN-1) allowed the reaction of arylboronic acids
with diphenyldiselenides at very low copper concentrations product can become the main product upon increasing the
(0.1 mol %) with high yields (Scheme 144, B).550 temperature of the reaction (Scheme 145, A).555 However, the
Immobilization of Cu(OAc)2 on the surface of function- formation of diaryl sulfide in other solvents can be selective. Of
alized polystyrene pyridine thiosemicarbazone was efficient in note, catalysis by CuCl2 and CuCl in DMSO without a ligand
the reaction of Ar(Het)B(OH)2 with Ph2Se2 in water (Scheme produces practically the same (close to quantitative) yield of
144, C).551 diaryl sulfide. Formation of a hydroxyl group occurs only in air.
Glycerol turned out to be a good medium for a CuI- In the Chan−Lam reaction, as in the Ullmann cross-
catalyzed reaction of Ar2Se2 with Ar′B(OH)2. Alves and co- coupling reactions with the formation of the C(sp2)−S bond,
workers demonstrated that the CuI/glycerol mixture could be various sulfur sources were used. Thus, in the reaction of
directly reused in sequential reactions with yields dropping arylboronic acids with a new disulforating reagent with an
from 90% to 71% by the fifth cycle (Scheme 144, D (1)).552 easily dissociating and electron-withdrawing acyl group under
Chem. Rev. 2022, 122, 16110−16293
Scheme 144
Chem. Rev. 2022, 122, 16110−16293
Scheme 145
mild conditions, asymmetric disulfides were formed in Dong and co-workers carried out Chan−Lam arylation of
moderate to very good yields (Scheme 145, B).556 arylthioureas under mild conditions, producing a large series of
Asymmetric diaryl selenides were synthesized in the reaction aryl isothioureas in good yields (Scheme 145, F).560 However,
of ArB(OH)2 with the electrophilic selenium derivative PhSeBr in the same reaction under harder conditions (Cu(OAc)2 (1.2
under catalysis by nanomagnetic CuFe2O4 particles in a equiv), DMF, 110 °C), diaryl sulfides are formed in good
recyclable PEG-400 medium (Scheme 145, C).557 yields (19 examples, 63−88%).561 Azole sulfides exhibit
Wang and co-workers used ethyl xanthogenate in the biological activity, and the azole sulfide motif is found in
reaction with ArB(OH)2. Diaryl sulfide was obtained in a many pharmaceuticals. The authors97 showed that the reaction
high yield under mild conditions under catalysis by CuCl of thiazolidine-2-thiones with aryl(heteryl)boronic acids,
without a ligand. The ligand-free reaction in methanol better catalyzed by Cu(acac)2 without a ligand, allowed the
preparation of azole-containing sulfides in high yields (Scheme
corresponds to the green chemistry concept (Scheme 145,
146, A). Ni and Pd acetylacetonates are inactive under these
D).558 In this reaction, a cross-coupling product formed at the
conditions.
first stage produces arylthiol upon hydrolysis in the presence of Dong and co-workers562 obtained interesting results when
KOH. In the next stage, a second C(sp2)−S bond is formed, studying Cu(OAc)2-catalyzed arylation of benzimidazoline-2-
allowing us to obtain both symmetric (9 examples, 73−96%) thiones with arylboronic acid. Depending on the conditions,
and unsymmetric (15 examples, 83−97%) diaryl sulfides. Low the reaction proceeded S-selectively or produced the products
yields were observed only in the reaction with p-NO2C6H4B- of arylation at both S and N atoms (Scheme 146, B).
(OH)2 (67%). Moreover, under alkaline conditions and at higher temper-
Disulfides were used as sulfur donors to obtain N-acetyl-S- atures, desulfurization with the formation of N-arylbenzimida-
arylcysteines (Scheme 145, E).559 zole occurred (Scheme 146, C).563 S-Arylation of 2-
Chem. Rev. 2022, 122, 16110−16293
Scheme 146
thioxoimidazolidin-4-ones produced S-aryl-substituted 2-thio- note, the reaction proceeded very fast within a few minutes
hydantoins under mild conditions. The compounds had a (Scheme 147, B).
certain anticancer activity (Scheme 146, D (1)).564 Addition- Compounds with a C−S−P(O) bond can be synthesized in
ally, arylation with boronic acid was performed for a selenium various ways. Tang, Xu, and co-workers proposed Cu-catalyzed
derivative (Scheme 146, D (2)).565 three-component reactions involving ArB(OH)2568 or ArN2X
Dong and co-workers carried out a reaction of arylboronic or Ar2IOTf569 (Scheme 148). Gram-scale quantities of PhS-
acids with tetraalkylthiuram disulfide to produce S-aryl P(X)(OEt)2 (X = O, S) were obtained in 98% yield in the
dithiocarbamates in good to excellent yields (Scheme 147, reaction with phenylboronic acid, in 80% yield with diphenyl
A).566 β-Furylboronic and β-tBu-vinylboronic acids did not iodonium, and in 83% yield with phenyldiazonium salt.
enter the reaction. Cu(III) supposedly participated in the Cao and co-workers570 carried out copper-catalyzed
reaction catalytic cycle. The reaction mechanism is proposed in trifluoromethylation in the Chan−Lam reaction using the
Figure 31. AgSCF3 silver salt (Scheme 149, A). In the case of arylboronic
Singh and co-workers567 carried out a reaction of acids with electron-withdrawing substituents, the yields
arylboronic acids with α-enolic dithioesters at room temper- decrease to moderate. The same happens in the reaction
ature, producing α-oxoketene S,S-acetals in high yields. Of with heteroarylboronic acids.
Chem. Rev. 2022, 122, 16110−16293
Scheme 147
However, both the Ni complex 571 and the copper

complex572 are capable of catalyzing the Ullmann571 and
Chan−Lam572 reactions with the ammonium salt [Me4N]-
[SCF3].
The reaction catalyzed by Cu(OTf)2/dtbpy at room
temperature proceeded with aryl(hetaryl)boronic acids in
good to high yields and with alkenylboronic acids in moderate
to good yields (Scheme 149, B).572 However, in the case of p-
phenylstyrylboronic acid, the use of O2 instead of atmospheric
oxygen increased the yield from 52% to 74%.
Duan and co-workers proposed an affordable and inex-
pensive method for introducing the CF3S group into the
aromatic ring. The reaction of arylboronic acids with available
Figure 31. Catalytic cycle for the Cu2O-catalyzed reaction of trifluoromethyl acetate and elemental sulfur, mediated by
arylboronic acid with tetraalkylthiuram disulfide. CuSCN under oxidizing conditions, produced the products in
moderate to good yields (Scheme 149, C (1)).573 The
following mechanism was suggested (Scheme 149, C (2)).
Qing and co-workers carried out Cu-catalyzed oxidative
trifluoromethylthiolation in a three-component reaction of
arylboronic acid, TMSCF3 and S8 (Scheme 149, D).574
Symmetric diaryl sulfides (selenides) can be produced not
only via the action of S8 or Se on ArX380 but also via the
reaction of S, Se, and Te with arylboronic acids (CuI, 1,10-
Phen·H2O, NH4BF4, DMSO·H2O, 100 °C, air) (Scheme 150,
A (1)). Pd and Ni were inactive in these reactions. However, a
similar reaction of tellurium with arylboronic acid, catalyzed by
palladium (PdCl2 (10 mol %)/1,10-Phen (10 mol %)),
proceeded with the formation of Ph2Te in 74% yield.575
Changing the reaction conditions led to the production of
diaryl disulfide or monoselenide (Scheme 150, A (2)).576
Figure 32. Catalytic cycle of the reaction of arylboronic acid with
A Cu(I)-catalyzed three-component reaction of arylboronic
ArSeCN catalyzed by Cu(II).
acid with elemental sulfur and halogen derivatives (aryl, benzyl,
Scheme 148
Chem. Rev. 2022, 122, 16110−16293
Scheme 149
alkyl) is not a Chan−Lam reaction but its continuation, since Liang, Deng, and co-workers carried out a three-component
the thiolating agent is formed from arylboronic acid and sulfur, oxidative reaction involving ArB(OH)2 and S8 and produced
and the method itself is a convenient route to asymmetric sulfenylimidazo[1,2-a]pyridines (Scheme 152, A).580
sulfides. This reaction was carried out in PEG with “ligandless” Liu, Zhou, and co-workers carried out direct selenylation of
CuI with high sulfide yields (Scheme 150, B).577 olefins in a three-component olefin−aryl(heteryl)boronic
A three-component Chan−Lam reaction catalyzed by a acid−selenium system under CuBr2 catalysis (Scheme 152,
heterogeneous Cu/Fe catalyst with phenylboronic acid, S8, and B).475 The reaction can proceed without the ligand, but its
aryl(heteryl)halide or benzyl halide leads to the production of presence improves the result. A radical mechanism is proposed
asymmetric sulfides in high yields (Scheme 150, C).578 The for the reaction.
Aryl thiocyanates were obtained via the Chan−Lam
catalyst and solvent were recycled, and in three cycles, a slight
reaction. For arylboronic acids with electron-withdrawing
decrease in the product yields was observed (98%, 88%, and
substituents (p-RC(O), p-NO2), a low yield was observed,
82%). Diphenyl sulfide, both in this reaction and in the and for styryl and cyclohexyl boronic acids, the reaction did
reaction without PhB(OH)2, is formed in 95% and 97% yields, not proceed at all (Scheme 153, A).582
respectively. In the selenylation reaction catalyzed by a mixture of two
Similarly, diaryl sulfides can be obtained by using ROX (X = salts�copper(II) acetate and silver carbonate�selenium
Tf, Ts, Ac, P(O)(OEt)2) phenol ethers instead of halides (23 cyanate was proposed as a selenating agent, which undergoes
examples, 75−93%). The reaction of PhOAc with PhB(OH)2, decyanation in the reaction not only with arylboronic acids but
catalyzed by CuI in the presence of S8 (NaOtBu, PEG200, 80 also with RSi(OR)3, RCO2H, and terminal alkynes (Scheme
°C) allows a quantitative yield of Ph2S. Instead of PhB(OH)2, 153, B).583 For terminal alkynes, 17 examples of the synthesis
Ph3SnCl can be used (Scheme 151).579 of products with 65−93% yields are
Chem. Rev. 2022, 122, 16110−16293
Scheme 150
Scheme 151
Scheme 152
shown. The following reaction mechanism is proposed (Figure We have already mentioned that various organoelement
32). However, a different sequence of stages is also possible. compounds can participate in the Chan−Lam-type cross-
Chem. Rev. 2022, 122, 16110−16293
Scheme 153
Scheme 154
coupling reaction. Of particular interest is the reaction of the R−S bond is formed, and in the second, the R−Ar bond is
Grignard reagent with diaryl(heteryl)disulfides, which was formed (Scheme 154, A).
The production of diaryl sulfides via the reaction of
carried out by Wang and co-workers.584 Of note, the possibility
arylboronic acids with arylsulfothioate (masked arylthioate)
of using the Grignard reagent as an electrophilic agent is under copper catalysis proceeds in an odorless way. However,
known.585,586 This reaction is catalyzed by either ferrocene or this reaction, along with diaryl sulfide, yields diaryl disulfide.
Pd complexes and yields various products: In the first case, the Jiang and co-workers found that the presence of CO2
Chem. Rev. 2022, 122, 16110−16293
Scheme 155
Scheme 156
suppressed disulfide formation (Scheme 154, B).587 A large The sulfenylation of aromatic and aliphatic boronic acids
with sulfonylhydrazides catalyzed by Cu(I) with a bpy ligand
series of compounds are obtained in moderate to good yields. was carried out by using a large series of substrates with good
Chem. Rev. 2022, 122, 16110−16293
Scheme 157
Scheme 158
Chem. Rev. 2022, 122, 16110−16293
Scheme 159
yields of unsymmetric sulfides (Scheme 154, C).588 Sulfo- The preparation of sulfones via the Chan−Lam reaction
nylhydrazides were shown to convert to thiosulfonate and catalyzed by Cu(OAc)2 without a ligand and base perfectly
disulfide (p-MeC6H4SO2SC6H4(p-Me) and p-MeC6H4S- demonstrates the advantages of this method. The reaction
SC6H4(p-Me)). proceeds in a green solvent at room temperature with
Simultaneously, the same idea, but using thiosulfonate RS- moderate to good yields, with a variety of substituents in
SO2R,386 also free from unpleasant odors, was implemented by both arylboronic acid and arylsulfonylhydrazide (Scheme 156,
Yoshida, Hosoya, and co-workers.589 Under milder conditions, B).592
the products were formed in high yields (Scheme 154, D). Under very mild conditions, diarylsulfones are formed in a
Thiosulfonates (and selenosulfonates)59 themselves, as copper-catalyzed reaction of arylboronic acid with arylsulfonyl
Taniguchi showed, were formed via the CuI/1,10-Phen- chloride (Scheme 156, C).593 The presence of water and
catalyzed oxidative coupling of thiols590 or dichalcogenides591 ligands plays an essential role.
with sodium sulfinate. In the absence of oxygen, the yield Along with ArB(OH)2, other organoelement compounds are
dropped sharply (Scheme 155).591 used. In one of the described reactions, the source of the Ph
The reaction of arylboronic acids with arylsulfonyl chloride group is not PhB(OH)2 but also Ph3SnCl. The reaction was
catalyzed by CuI/1,10-Phen and PPh3 in the presence of carried out with S8 activated by KOH and KF in DMF at 80
atmospheric oxygen leads to the formation of asymmetric °C, with the participation of PhI under catalysis by supported
sulfides. It is assumed that ArSO2Cl, upon reacting with PPh3, Cu(II) without ligands. In both cases, Ph2S was formed in a
forms a disulfide, which reacts with Cu(I) (Scheme 156, A).581 quantitative yield. High yields were also observed when varying
Chem. Rev. 2022, 122, 16110−16293
Scheme 160
the substituent and when using aryl bromides and aryl chlorides with organozinc compounds in the presence of CuI
chlorides, although in the latter case at a longer reaction and PPh3 as a reducing agent can be mentioned (Scheme 158,
time. For the ArB(OH)2 reaction, not only Cu(II) but also B).601
Cu(I) were used. In both cases, the catalyst could be recycled To obtain sulfones, as in the case of palladium, the usage of
repeatedly and retained its activity in eight cycles.594 the SO2 molecule was most attractive, as was shown by Wu,
It was shown that all three aryl groups are involved in the Beller, and Li.602 The catalysis in this reaction was carried out
reaction of Ar3Bi with diaryl disulfides catalyzed by Cu- by CuCl2. Arylsulfonamides were formed in moderate to good
(OAc)2/1,10-phen. Asymmetric diaryl sulfides were formed in yields (Scheme 158, C), with the mechanism shown in Figure
good yields (Scheme 157, A).595 33.
Formation of symmetric aryl selenides in the reaction of Wang and co-workers carried out a Cu(OAc)2/Xphos-
Ar3Bi with elemental selenium proceeds in a similar way catalyzed three-component reaction of triethoxysilane with
(Scheme 157, B).596 A Cu(OAc)2/Py-catalyzed reaction of DABSO and hydrazines to produce a large family of
tricyclopropyl bismuth with aromatic thiols is described. Note biologically interesting sulfonylamides in moderate to good
that similar processes for (c-Pr)3Bi were performed for yields (Scheme 158, D). 592 A similar reaction with
amination and arylation. A large series of arylcyclopropyl diethoxysilane for the four studied compounds (Ar = Ph, p-
sulfides were obtained in moderate to high yields. As a Tol, β-naphthyl, p-ClC6H4) proceeded with 93−99% yields of
byproduct, Ar2S2 was formed (Scheme 157, C).597 arylsulfonylamides.
Among the new works on bismuth, S-arylation of diary- 4.2.3. C−H Functionalization. 4.2.3.1. Formation of
ldisulfides595 and azole-2-thiones598 by Ar3Bi and reactions of C(sp2)−S (Se) Bonds. Copper is an important alternative to
organostannanes with diaryldisulfides and electrophilic N- noble metals not only in Ullmann coupling but also in C−H
sulfenyl succinimide under catalysis by ligandless CuCl should activation reactions.44,45
be noted.599 Direct functionalization of arenes via copper-catalyzed
A three-component reaction with the participation of reactions begins later than via reactions catalyzed by complexes
Ph3SnCl and S8 was carried out to obtain asymmetric sulfides. of noble metals, and the sulfenylation reaction is not an
Under these conditions, the reaction of PhI and S8 produces exception. The reaction was first carried out by Yu and co-
Ph2S in a quantitative yield (Scheme 158, A).600 workers in 2006 with PhSH and MeSSMe,603 and then Qing
There are other, more exotic, methods for producing sulfides and co-workers continued the work by demonstrating
(thioesters). For example, the reaction of aryl(heteryl)sulfonyl methylthiolation with DMSO as a source of the MeS group.604
Chem. Rev. 2022, 122, 16110−16293
Scheme 161
Direct C(sp2)−H thiolation is undoubtedly a more efficient ditellurides (Scheme 160, A).608 In the case of selenium and
and atom-economical process than the Buchwald−Hartwig, sulfur, the reaction proceeded at two positions with yields
Ullmann, or Chan−Lam reactions. However, such reactions ranging from good to high. In the case of tellurium, only a
proceed with a certain type of arene, either electron-rich or monosubstituted product was formed in the reaction. The
containing a C(sp2)−H bond capable of easy deprotonation. yields were lower than for sulfur and selenium, and the
Conventional “nonactivated” arenas require the presence of a conditions were more severe (oxidizing agent AgOAc (1.3
so-called directing group, which, due to coordination with the equiv), additive KF (1 equiv), and DMSO).
catalyst metal, provides metallization at the ortho-position. We Shi and co-workers carried out thiolation of a large series of
will discuss such reactions first. nonactivated heteroarenes with DG under the action of
During the period of interest, such a reaction was carried out disulfides catalyzed by Cu(OAc)2 without a ligand (Scheme
by Daugulis and co-workers (2012).605 They used 8-amino- 160, B).609
quinoline as a directing group, which turned out to be not only Shi, Wu, and co-workers610 carried out a similar reaction
easily removable but also extremely efficient. Disulfides were using a cheaper source of sulfur, elemental sulfur, which, in the
used as a source of RS groups (Scheme 159, A). The reaction absence of an alkyl halide, led to the formation of
at unsubstituted ortho-positions proceeded with the formation benzoisothiazolones (the first example of the formation of a
of a disubstituted product. The reaction with diaryldiselenides new N−S bond in the CH/CS reaction). Compounds were
proceeds in a similar way (Scheme 159, B).606 obtained with moderate to good and even high yields (Scheme
Similar to sulfenylation, the Cu(OTf)2-catalyzed reaction of 160, C). The ring opening or oxidation of sulfur allows a
N-acylaminoquinoline with Ar2Se2 proceeds regioselectively at variety of organosulfur derivatives to be obtained.
position 5 (Scheme 159, C).607 A radical reaction mechanism By using 8-aminoquinoline and copper(II) acetate with the
is assumed. With another similar directing group, the result was bathophen ligand, Liu and co-workers carried out the reaction
slightly worse than for Scheme 159, D.605 with aromatic and aliphatic thiols (Scheme 161, A).611 The
Kumar and co-workers carried out Cu(OAc)2-catalyzed reaction with an excess of thiol yielded a dithiolated product
arylchalcogenation of ferroceneamide containing DG (8- (with rare exceptions, when only the monosubstituted product
aminoquinoline) by using aryl disulfides, diselenides, and was formed). The synthesis of 30 compounds was carried out.
Chem. Rev. 2022, 122, 16110−16293
Scheme 162
The substrate scope was quite broad, and the reaction showed which can be useful for the preparation of chiral planar ligands
good functional group tolerance. (Scheme 161, C).613
Another variant of the bidentate directing group was Qiu, Yin, Kambe, and co-workers614 studied Cu-mediated
proposed by Liu, Chen, and co-workers612 in the Cu(II)- direct thiolation of carbazole derivatives carrying the easily
mediated C(sp2)−H sulfonation reaction under the action of removable 9-(pyrimidin-2-yl) group as a directing group under
2-mercaptobenzimidazoles (Scheme 161, B). The reaction was the action of diaryl(dialkyl)disulfide (Scheme 162, A).
It should be noted that the reaction without a directing
accompanied by annelation, yielding polycyclic fused imidazo-
group proceeds nonregioselectively and with a lower yield. The
[2,1-b][1,3] thiazinones. Varying the substituents in both
same DG was successfully used in the reactions of other N-
reagents allowed us to obtain a variety of derivatives heterocycles. However, the reaction was not catalytic and
(approximately 30 compounds) in moderate to good yields. required a high temperature.
Thus, complex synthetic compounds with potential biological The same directing group was used by Ackermann and co-
activity can be obtained in one step from available precursors. workers to chalcogenize indolines and indoles.615 The
The reaction of ferrocene with a chiral oxazoline group processes were selective in the case of indolines, at position
yields a monothiolation product with high diastereoselectivity, 7, and in the case of indoles, at position 2, for both sulfur and
Chem. Rev. 2022, 122, 16110−16293
selenium. Under the optimized conditions, a large series of dichalcogenides with the same catalyst but atmospheric oxygen
indolyl sulfides and selenides with the ArS(Se) group at as an oxidizer proceeds peri-selectively619 (Scheme 163, B).
position 7 were obtained. Of note, the reaction conditions An interesting result in the study of C−H functionalization
were milder than those for carbazole (Scheme 162, B). Under was obtained by Ackermann and co-workers.620 In a reaction
the same conditions, the reaction with indole proceeds catalyzed by Cu(I) with a compound in which two types of
selectively at position 2 (Scheme 162, C). coordination (N,N-bidentate or with oxygen) are possible,
Since the resulting indoline derivatives are readily oxidized copper preferred a weaker interaction (Scheme 164, A).
to indole derivatives and the directing group can be removed, Depending on the nature of the base and the reaction time,
both indole regioisomers, which are of interest as natural and thiolation of N,O-directed benzamide proceeds selectively as
biologically active compounds, become available. The authors mono- or disubstitution (however, the oxidizing agent also
proposed the reaction mechanism upon demonstrating that changes). TEMPO does not affect the product yield (Scheme
radical traps slowed or even stopped the reaction. In this 164, B).621
mechanism, an attractive explanation of the production of Cu-catalyzed sulfenylation of N-aryl-7-azaindoles with
Cu(III) is given. Therefore, the catalytic cycle is proposed by disulfides and diselenides was carried out (Scheme 164,
the authors (Figure 34). C).622 Diaryl sulfides and selenides containing the phenol
group were produced in a Cu(OAc)2-mediated reaction of
direct introduction of the YAr group into the ortho position of
phenol containing a phenanthroline auxiliary under the action
of (ArY)2 (Scheme 164, D).623
Electron-rich arenes undergo direct thiolation catalyzed by
copper salts. An example is the reaction of methoxy-substituted
arenes with diaryl sulfides carried out by Cheng and co-
workers, catalyzed by CuI in the presence of O2 in DMF at 120
°C, in which the products�asymmetric diaryl sulfides�were
produced in a yield up to 98% (Scheme 165, A).624
A CuI-catalyzed thiolation of pyrrole was carried out, and it
predominantly proceeded at position 2 (Scheme 165, B).625
Figure 33. Synthesis of arylsulfonamides. The imidazo[2,1-b]thiazole motif is found in many natural and
biologically active molecules. Cao and co-workers studied the
sulfenylation of 3-methyl-6-phenylimidazo[2,1-b]thiazole
under copper catalysis with alkyl and aryl(heteroaryl)thiols
and showed that the CS bond was formed regioselectively at
the fifth position (Scheme 165, C).626 The reaction can be
carried out with disulfides as sulfenylating agents.
Zheng, Qi, and co-workers proposed a convenient protocol
for the selective thiolation of imidazo[1,2-a]pyridines with a
wide variety of thiols using O2 as an oxidizing agent, with very
good yields. Nineteen compounds were obtained in 81−92%
yields, and two compounds in the reaction with 1,3-
pyrimidinethiol were obtained in 72% and 73% yields (Scheme
165, D).627
At the same time, CaO and co-workers carried out this
reaction under CuI−O2 catalysis in DMSO at 100 °C, with the
same regioselectivity at position 3 and similar yields (Scheme
165, E, Figure 36).628
Zhou and co-workers carried out the reaction with PhYYPh
Figure 34. Catalytic cycle of Cu(II)-catalyzed thiolation of the C−H (Y = S, Se) under CuI catalysis for a large number of
bond with Ph2S2. imidazopyridines, imidazopyrimidines (Scheme 165, F (1)),
indoles, and pyrrolo[2,3-b]pyridines (Scheme 165, F (2)).629
Yin and co-workers616 carried out Cu-mediated dichalcoge- CuI/SeO2-catalyzed selenylation of 1-H-indole and imidazo-
nide-induced chalcogen introduction into 8-aminoquinoline [1,2-a]pyridines at position 3 was carried out with Ph2Se2
with an aliphatic amide moiety at distal position 5 (Scheme under the action of ultrasound (Scheme 165, G).630 Under the
163, A). With ditellurides, the reaction proceeds with a low action of ultrasound, the reaction proceeded in minutes. The
yield, but for disulfides and diselenides, the yields vary from antioxidant activity of the obtained compounds was studied.
good to high. It is assumed that this orientation is provided by The products of selenylation of imidazoheterocycles and
the anionic copper complex being formed and electron transfer indoles were also obtained in a copper-catalyzed three-
(SET) with the appearance of a radical (Figure 35). component reaction with Se powder (Scheme 165, H).631
The sensitivity of the regioselectivity of the C−H/C−S CuI-catalyzed direct CH-sulfenylation of seven heterocycles
formation of 1-naphthylamines to the reaction conditions is and 9-deazapurines under the action of R2S2 is described in
surprising. Thus, the reaction with a picolinamide auxiliary Scheme 166, A.632 9-Deazapurines required a ligand. Purine
with RSO2Cl or RSO2Na, catalyzed by Cu(OAc)2 with itself did not react under these conditions.
Cu(OAc)2 or Mn(OAc)2 as an oxidizing agent proceeds at a Direct thiolation of xanthines with disulfides was carried out
remote position,617,618 whereas the same reaction with under catalysis by Cu(OAc)2 and oxidizing conditions, and the
Chem. Rev. 2022, 122, 16110−16293
Scheme 163
reaction proceeded without a base (Scheme 166, B).633 Under aliphatic thiols. Of the seven tested ligands, bpy demonstrated
these conditions, indole reacted with a good yield (at position the best results (Scheme 169, A).639 Of the possible reaction
3, yield 70%), and benzothiazole and 4,5-dimethylthiazole routes with the formation of copper sulfide ([CuSR]bpy) or a
reacted in high yields (95% and 91%, respectively). The benzothiazolyl derivative of copper in the first stage, the
presence of AgOAc plays a double role: OAc− mediates authors chose the first variant as more thermodynamically
deprotonation, whereas Ag+/O2 is an excellent oxidizing favorable. In addition, it was shown that the reaction of
system. benzothiazole with CuSPh under these conditions led to a
Under the action of Ph2S2 (Ph2Se2) and catalysis by thiolation product with a 90% yield. The proposed mechanism
Cu(OAc)2 (20 mol %), direct regioselective thiolation involved the metathesis of the σ-bond with further hydride
(selenylation) of azaheteroaromatic N-oxides proceeds elimination or oxidation with oxygen. The latter was very likely
(Scheme 167, A).634 since the yield increased upon increasing the O2 content.
Alves and co-workers studied the direct selenylation of However, in an O2 atmosphere, the yield dropped sharply,
anilines under the action of diphenyldiselenides catalyzed by possibly due to the formation of disulfide.
CuI in DMSO in air. A large series of para-selenyl-substituted Direct CH thiolation of substituted benzothiazoles and
anilines were obtained in moderate to high yields (Scheme benzoxazole with aryl and alkyl thiols was carried out under
167, B).635 When the para-position is occupied, the reaction is
catalysis by copper carbene complexes. Of the four tested
directed to ortho, but the product yield is lower.
carbene complexes, the IprCuI complex demonstrated the
In continuation of this work, the synthesis of selenated
highest activity. The reaction proceeded with moderate to
pyrazoles636 was carried out via a three-component reaction of
condensation/selenylation of the C−H bond with the good yields (22−82%). The highest yields were observed for
participation of hydrazine, dione, and diselenide under unsubstituted heterocycles: 81% for benzothiazole and almost
CuBr/bpy catalysis in DMSO (Scheme 167, C). quantitative for benzoxazole.640
A one-pot process for producing substituted imidazo[1,2- Liu and co-workers proposed another variant of such a
a]pyridines and their selenylation at position 3 (17 reaction involving Cu(OAc)2 and CuO for a variety of
compounds) was described by Schumacher, Lenardão, and heterocycles. The products were obtained in moderate to good
co-workers. The output is lower with S, and with Te, the yields, which were higher for alkyl thiols than thiophenols
reaction does not proceed at all (Scheme 168, A).637 (Scheme 169, B).641
A multicomponent reaction catalyzed by CuI in the presence By the example of reactions of heteroarenes with thiols,
of BF3·OEt2 yielded sulfenylimidazo[1,2-a]pyridines in mod- good results were achieved with a combination of the Lewis
erate to high yields (38−91%) (Scheme 168, B).638 acid (catalyst) and Cu(OAc)2 (cocatalyst in an equivalent
On the other hand, heteroarenes with a sufficiently acidic amount). The model reaction of benzothiazole with butylthiol
CH bond for which organocopper compounds are formed as a proceeded without a base with yields higher than 90% for
result of deprotonation under the action of a base undergo AgOCOCF3 (>99%), NiCl2 (98%), and Zn(OTf)2 (92%)
direct thiolation. Huang, Liu, and co-workers studied a CuI- (Scheme 169, C).642 Methylthiolation was carried out using a
promoted reaction of benzothiazoles with aromatic and AgF/Cu(OAc)2 catalytic system at 140 °C (Scheme 169, D).
Chem. Rev. 2022, 122, 16110−16293
Scheme 164
Earlier, benzoxazole thiolation was carried out with the According to the proposed mechanism, disproportionation of
participation of Ar2S2 (CuI/bpy, Cs2CO3, DMF, O2, 80 °C, 2 Cu(II) results in the formation of Cu(III) (Scheme 170, D).
h). The yield of 2-phenylthiobenzooxazole was 81%, which was The reaction of azoles with thiols or DMSO, mediated by
higher than the moderate (42%) yield in the reaction with Cu(OAc)2, is accelerated in the presence of the Lewis acids
PhSH (Scheme 170, A).643 Ag(I), Ni(II), Au(I), etc.642
Zeni and co-workers carried out a heterogeneous variant of In the case of pentafluorobenzene, which also had an
the reaction of thiazole and benzothiazoles with disulfides and “acidic” CH bond, as shown by Shi and co-workers,646 the
diselenides under catalysis by CuO nanoparticles (Scheme thiolation reaction with thiophenols or diaryldisulfides,
170, B).644 The thiazole reaction proceeded with a significantly catalyzed by Cu(I) in the presence of a base and O2,
lower yield (45% for S and 35% for Se). Since the addition of proceeded under mild conditions, producing a bisaryl
TEMPO did not stop the reaction, the authors considered the thiolation product in moderate to high yields. Thus, in this
radical mechanism unlikely. reaction, both thiolation at the activated C−H bond and SNAr
The Cu(OAc)2-catalyzed reaction of “acidic” azoles with substitution at the C−F bond occurred (Scheme 171).
diphenyl disulfides and diphenyl diselenides proceeds with For insufficient electron-donating arenes, Lee and co-
good results without a base and ligands (Scheme 170, C).645 workers proposed a two-stage reaction, in which boronation
Chem. Rev. 2022, 122, 16110−16293
Scheme 165
Chem. Rev. 2022, 122, 16110−16293
Scheme 165. continued
occurred at the first stage catalyzed by iridium, and cross- out under CuCl (bpy) catalysis (Scheme 172, A). In the case
of Se and Te, the reaction proceeded with the same yields.
coupling catalyzed by CuCl occurred at the second stage.647
A similar strategy was applied in the reaction with thiol and
The second stage, the Chan−Lam-type reaction, was carried diselenide (Scheme 172, B).648 Under microwave irradiation,
Chem. Rev. 2022, 122, 16110−16293
4.2.3.2. Reactions Using Other Sulfur/Selenium Sources.

C−H activation of electron-donating arenes and heteroarenes
with the formation of symmetric diaryl(heteroaryl)sulfides
occurs under the action of elemental chalcogenides and CuTC
catalysis in DMSO using air oxygen as an oxidizing agent
(Scheme 174).656
Under these conditions, the reaction with benzimidazole and
benzothiazole does not proceed. Selenylation of imidazo[1,5-
a]pyridine produces a mixture of mono- and diselenides, the
latter being converted into monoselenide in excess of the
starting compound under CuBr catalysis.
A three-component reaction of aryl iodide, indole, and
selenium, catalyzed by CuO (10−20 mol %), is new to the
chemistry of selenium and results in the formation of two
C(sp2)−Se bonds and a selenyl derivative of indole in high
yields (Scheme 175, A).657 Such indole derivatives inhibit
tubulin polymerization and thus can be considered antitumor
Figure 35. Remote thiolation of 8-aminoquinoline with an aliphatic agents. A similar reaction was carried out in the intramolecular
amido group. version to obtain benzoselenopheno[3,2-b]indoles in a very
high yield (R = H, 97%) (Scheme 175, B).657
An intramolecular process with the cleavage of C(sp2)−Br
and C(sp2)−H bonds and the formation of two C(sp2)−Se
bonds proceeds during the selenylation of 2-(2-bromophenyl)-
imidazo[1,2-a]pyridines with selenium powder under catalysis
by CuI (Scheme 175, C).658
Formation of imidazo[1,2-a]-pyridine/benzo[b]-
selenophenes proceeds without a base and ligand and does
not require a special oxidizing agent. Most interestingly, the
reaction was completely inhibited by the addition of TEMPO.
The authors presented a lot of evidence in favor of a radical
reaction mechanism.
Searching for a reaction that met modern requirements
(environmentally friendly and economical), Deng and co-
Figure 36. Transformation of CH → CS in imidazopyridines. workers659 studied the possibility of thiolation in a three-
component reaction of electron-rich arenes with aryl iodides
and elemental sulfur in water (Scheme 176 (1)). It was shown
the reaction time for obtaining sulfides was reduced from 24 to that Cu(OTf)2/1,10-Phen catalyzed this reaction with β-
2.5 h. The second stage with thiols was carried out under naphthol in good to high yields (an exception was the reaction
Cu(OAc)2/Py catalysis in DMF (MW, 135 °C).649 with 4-I-C6H4I, where the yield was 40%).
Another variant of CH bond activation in weakly donating Heteroaromatic iodides also enter the reaction, although the
arenes uses a two-step bromination procedure (NBS, FeCl3) yield depends strongly on the nature of the heteroarene.
followed by Cu-catalyzed cross-coupling with RSH (Scheme Nevertheless, even alkyl iodides can produce the product,
172, C).650 although the yield is reduced significantly (from 21 to 55%).
Thiomaleimide has biological activity and is often used in Substituents in naphthol reduced the yield, for example, for Br
organic synthesis. By the example of maleimides and 3- at positions 6 and 7 to 60% and 68%, respectively.
indolylmaleimides, Zhao and co-workers showed that their thio The synthesis of 2-phenylimidazo[1,2-a]pyridine thio
derivatives could be efficiently obtained in good yields via derivatives proceeded well under these conditions (Scheme
direct thiolation catalyzed by copper (CuI (20 mol %) − HBF4 176 (2)). Although the catalytic cycle proposed by the authors
(1 equiv), DMSO, 120 °C, air, Figure 37).651 raises many questions, it clearly demonstrates the complexity
Zhang and co-workers carried out sulfenylation of the of the system in the presence of different anions (Figure 38).
C(sp2)−H vinyl bond under the action of diaryldisulfides, In 2016, another work on the arylsulfenylation of
catalyzed by Cu(OTf)2 in the presence of an equimolar imidazopyridines, also via a trimolecular process with the
amount of I2. The reaction proceeded stereoselectively with participation of S8, was published. The reaction proceeded in
the formation of the E-isomer (Scheme 172, D).652 The DMF under Cu(I) catalysis (Scheme 177, A).660 A large series
reaction mechanism was supposed to be radical because in the of compounds were obtained, many with yields >90%. The
presence of 2.5 equiv of TEMPO the product, was not formed. radical mechanism was ruled out since the addition of TEMPO
A significant number of works are dedicated to the did not change the product yield (87%). It was assumed that
preparation of alkynyl sulfides via the reaction of terminal diphenyl disulfide could be involved in the reaction.
alkynes catalyzed by CuX (including heterogenized alkynes) in Guo, Zhao, Ma, and co-workers applied a similar method-
the presence of an oxidizing agent.653−655 In these studies, the ology and carried out a three-component reaction with sulfur
authors solved the problem of competition with Glaser or selenium powders to chalcogenate imidazo heterocycles
coupling and the use of a cheap oxidizer such as O2 (Scheme with coumarin triflate using CuO as a catalyst (Scheme 177,
173). B).661
Chem. Rev. 2022, 122, 16110−16293
Scheme 166
Disulfenylation of imidazo[1,2-a]pyridines with elemental A three-component reaction of the synthesis of flavone

sulfur in the presence of aryl halides was carried out via a selenide and sulfide derivatives using KSeCN and KSCN as
trimolecular reaction (Scheme 177, C).662 Intramolecular sulfur and selenium surrogates was carried out (Scheme
cyclization of haloimidazo[1,2-a]pyridines in the presence of 180).667 According to the authors, the reaction proceeded via
S8 was carried out with the formation of benzothieno- the formation of ArYCN with the further formation of the
imidazo[1,2-a]pyridines in up to 99% yield (Scheme 177, D). copper complex ArYCuI(CN), which reacted with the flavone.
A CuCl2-catalyzed reaction of iodobenzenes with benzo- 2-Aminothiazoles were obtained in a Cu(OTf)2-catalyzed
thiazole in the presence of selenium powder produces a reaction of arylthioisocyanates with amines (Scheme 181).668
coupling product in moderate to high yields (19 examples, 32− Of note, the reaction catalyzed by ligandless copper
91%). Similarly, the reaction of iodobenzene with substituted demonstrates product yields comparable to those obtained in
azoles (benzothiazole and benzimidazole) proceeded with the reaction catalyzed by Pd(OAc)2/phen.
modest to high yields (12 examples, 15−93%). The reaction is Sodium sulfonyl chlorides and arylsulfinates can act as aryl
scalable (Scheme 178, A).663 It was shown that the reaction thiol surrogates, particularly in direct CH sulfenylation.669
did not proceed with PhSeCu, and it was suppressed by the Such reactions with electron-rich arenes such as indole can
addition of TEMPO and oxygen. proceed without a metal catalyst. In other cases, for example, in
A photoinduced Cu-catalyzed three-component reaction of the reaction of sulfonyl chloride with imidazopyridine, a
thiolation of the CH bond in benzothiazole with sulfur copper catalyst is required (Scheme 182, A).670 Formation of
(selenium) proceeds at room temperature (Scheme 178, B).664 the C−S bond in imidazo[1,2-a]pyridines via C−H function-
Thiazole also reacts (with sulfur and selenium). The proposed alization has been the subject of numerous studies due to its
mechanism involves the formation of diaryldisulfide (selenide), application in medicinal chemistry (see the review671).
which reacts with benzothiazole. A reaction of indole with sodium sulfinate, catalyzed by
The most economical and efficient way of introducing sulfur copper acetate with D-glucosamine as a ligand in the DMSO−
or selenium into the enamine molecule at the vinyl position is NH4I system, forms the corresponding sulfides (Scheme 182,
the reaction with sulfur powder or selenium, which results in B).672 With sodium arylsulfinate, this and similar reactions
the formation of sulfides and selenides in high yields under proceed under the action of the I2/PPh3 catalytic system.673,674
catalysis by CuBr on air (Scheme 178, C).665 However, the reaction catalyzed by CuBr2 also yields good
Sulfenylation (thiolation) of imidazo[1,2-a]pyridines in the results.675 The authors676 obtained the products of thiolation
reaction of C−H functionalization under the action of of indoles with RSO2Cl in argon in high yields and, therefore,
Na2S2O3 and alkyl halides and aryl iodides was studied proposed an electrophilic substitution mechanism (Scheme
(Scheme 179).666 182, C). The Cu−PPh3 system promotes the sulfenylation of
A radical reaction mechanism was proposed. quinones by ArSO2Cl (Scheme 183).677
Chem. Rev. 2022, 122, 16110−16293
Scheme 167
Scheme 168
Liu and co-workers described the direct thiolation of derivatives are formed upon the presence of donor groups,
electron-rich arenes by arylsulfonyl hydrazides mediated by as well as a CF3 group, in the para-position of the sulfonating
Cu(OTf)2 (Scheme 184, A).678 A mixture of di- and agent. The reaction is also possible for other electron-rich
monosubstituted compounds is formed. Monosubstituted arenes.
Chem. Rev. 2022, 122, 16110−16293
Scheme 169
A reaction of terminal alkenes with sulfonyl hydrazides Methylthiolation of arenes and heteroarenes with pyridine or
catalyzed by CuCl/LiBr in air yields vinyl sulfones (Scheme pyrimidine as a directing group was carried out using the
184, B (1)).89 Under the same conditions, but upon replacing Cu(OAc)2 (1 equiv)−DMSO system (Scheme 186).679 The
LiBr with DABCO, oxidative sulfenylation of indole and other silver salt AgSCF3 was used to prepare benzyltrifluoromethyl
electron-rich aromatic compounds was carried out under the sulfides. The reaction produces a benzyl radical (Scheme
catalysis of CuCl (5−10 mol %), producing the corresponding 187).680
A CuI-catalyzed chalcogenation of the C(sp)−H bond of
sulfides (Scheme 184, B (2)).89
alkynes by dichalcogenides resulting in the production of 3-
Three types of substrates were subjected to Cu(OAc)2-
(phenyl-selanyl)prop-2-yn-1-yl benzoate, which exhibited high
catalyzed sulfenylation with S-aryl arenesulfonothioate: arenes, in vitro activity against glioblastoma cancer cells, should also
heteroarenes with Py as DG, and electron-rich heteroarenes be mentioned (Scheme 188).681
(N-alkyl indoles and 2-arylimidazopyridines) (Scheme 185, 4.2.3.3. Formation of Sulfones. Above, we considered the
(1)-(2)).88 With N-methyl-5-nitroindole, the reaction did not production of sulfones as an example of reactions with the
proceed (Scheme 185, (3)). formation of a carbon−sulfur bond. However, sulfones are an
Chem. Rev. 2022, 122, 16110−16293
Scheme 170
Scheme 171 out under the action of sulfonating agents with different
polarities but under oxidizing conditions.
Direct sulfonylation of arenes proceeds in the presence of a
directing group in them. Below, there are examples of such
reactions involving the electrophilic sulfonating agent RSO2Cl.
Cu(OAc)2-catalyzed sulfonylation of indolines with arylsul-
fonyl chlorides using pyrimidyl DG proceeded in hexafluor-
oisopropanol (HFIP), with high regioselectivity at position 7
(Scheme 189, A).102 Additionally, it has been shown that the
reaction proceeds with the formation of RSO2•. A large series
important class of S-containing compounds, and the C(sp2)− of compounds were obtained.
SO2R fragment is found in many biologically active molecules, Direct sulfonylation of a large number of arenes was carried
drugs, and functional materials. Much attention is currently out with another DG (PIP), also under catalysis by Cu(OAc)2
being paid to the synthesis of sulfones. but upon using the nucleophilic sulfonating agent sodium
One of the most efficient methods for their preparation is arylsulfinate in the presence of oxidant (Scheme 189, B).682 A
the direct sulfonation of arenes. This reaction can be carried catalytic cycle with the participation of Cu(III) was proposed.
Chem. Rev. 2022, 122, 16110−16293
Scheme 172
The reaction proceeded selectively at the ortho-position C(sp2)−H bond and participates in disproportionation,
(Figure 39). leading to the formation of Cu(I) and Cu(III).
Amidoxazoline proved to be an efficient DG in the reaction The success of the sulfonylation of C(sp2)−H and C(sp3)−
of arenes and heteroarenes with sodium or lithium H bonds is described in a previous review.100 A comparison of
arylsulfinate, catalyzed by Cu(OAc)2 in trifluoroethanol the influence of different targeting groups on the yield of the
(TFE) (Scheme 190, A).104 The reaction was carried out sulfonated product was carried out (Scheme 190, C).
without an oxidizing agent since Cu(OAc)2 was taken in Remote sulfonylation of aminoquinolines with sodium aryl
excess. sulfinate in the presence of the oxidizing agent TBPB was
The reaction with the same sulfonating agent in excess observed at position C-5 (Scheme 191, A).684
Cu(OAc)2 in the presence of an easily removable bidentate A radical mechanism was assumed. If the reaction with
DG (8-aminoquinoline) proceeds in a similar way at the ortho sodium arylsulfinate, as shown above, proceeded at the ortho-
position (Scheme 190, B).683 The authors proposed a position of benzoic acid derivatives, similar to the reactions
mechanism where Cu(OAc)2 plays two roles: it activates the directed by pip and the amido-oxazoline group, then in this
Chem. Rev. 2022, 122, 16110−16293
Figure 37. Thiolation products of maleimides and 3-indolylmaleimides.
Scheme 173
case, the sulfonyl group entered position 5 (remote position). Particular attention was paid to the sulfonylation of 8-
This is an example of peroxide-controlled regiodivergence. amidoquinolines under the action of arylsulfonyl chloride since
Chem. Rev. 2022, 122, 16110−16293
Scheme 174
Scheme 175
the sulfonation was regiodivergent, depending on the chloride producing higher yields than the electron-withdrawing
conditions. substituents. Under the same conditions, the reaction of
A similar result was obtained by other authors (Scheme 191, isoquinoline N-oxide proceeds in the same way with high
B)676,685−688 as well as upon using sulfonylhydrazide (Scheme yields (88%) but with a different regioselectivity (in the meta-
191, C).689 position with respect to nitrogen). According to these results,
The authors’ opinions on the mechanism of these reactions the authors propose a mechanism involving metalation,
differ, although the majority favors the radical reaction oxidative addition with the formation of Cu(III), and reductive
mechanism.686 In addition to the influence of DG, the elimination.
possibility of the conversion of C(sp2)−H to C(sp2)−SO2R Sulfonylation of quinoline N-oxides under the action of
is affected by the electron donation of the molecule itself. sodium sulfinate and an oxidizing agent initiating RSO2•
Wu and co-workers carried out a quinoline N-oxide radicals leads to the formation of sulfonylated quinoline.691
sulfonylation reaction catalyzed by CuI without a ligand Sulfonation of the CH bond was carried out using N-
(Scheme 192, A).690 The reaction yields range from good to alkoxyamides with the PyO-directing group and TosMIC (p-
high, with the electron-donating substituents in sulfonyl tosylmethyl isocyanide). By many examples, it was shown that
Chem. Rev. 2022, 122, 16110−16293
Scheme 176
The preparation of sulfones in a copper-catalyzed reaction of

oxime acetate with sodium sulfinate was described (Scheme
193, B). The process looked like a C−H activation, but the
mechanism suggested a radical addition of RSO2• to the
enamide intermediate.694
2-Sulfonylbenzofurans were obtained via a cascade reaction
with trans-2-hydroxycinnamic acids and sodium sulfinates
mediated by CuCl2 and the oxidizing agent AgTFA (Scheme
194, A).695 A large series of furyl sulfones were obtained
mainly in good yields. The authors considered the reaction
mechanism with the participation of a sulfonyl cation, which
was formed stepwise upon the oxidation of Ag(I), while copper
participated in the cyclization without affecting sulfur.
Copper-catalyzed direct oxidative formation of (E)-vinyl
sulfones from styrenes in moderate to good yields in which air
oxygen acted as an oxidizing agent was described (Scheme 194,
B).696 The proposed mechanism included the addition of
RSO2• to a multiple bond, oxidation of the resulting radical to
a cation, and deprotonation under the action of DMAP.
4.3. Other Metals in C−Z Cross-Coupling Reactions
Figure 38. Catalytic cycle with Cu(III) participation in the thiolation
process. The use of metals such as nickel, cobalt, and iron as catalysts
for organic synthesis began to be studied actively at the
beginning of the 21st century, although separate examples of
sulfonation proceeded with good yields in the presence of
their activity were discovered much earlier. However, to date,
various substituents in both reagents (Scheme 192, B).692
The reaction of aryl ketones with sodium arylsulfinate these metals do not compete with copper. The same can be
catalyzed by CuBr2 in the presence of DBU proceeds with said for noble metals such as rhodium or ruthenium. Cross-
direct functionalization of the C(sp3)−H bond with moderate coupling reactions, Chan−Lam reactions, or oxidative
to very high yields under mild conditions (Scheme 193, A).693 functionalization of the CH bond carried out with these
Of note, the reaction requires nitrogen-containing ligands only metals do not demonstrate particular advantages over similar
for ketones with electron-donating groups but not for those reactions with palladium or copper. However, these metals
with electron-withdrawing groups. Since TEMPO inhibits and (such as iridium or ruthenium) have their own area of
even stops the reaction, a radical mechanism is proposed. dominance, that is, photoinduced reactions. For the sake of
Chem. Rev. 2022, 122, 16110−16293
Scheme 177
completeness, we will briefly discuss catalytic reactions In 2007, good results were obtained in the S-cross-coupling
involving these metals. with heterocyclic carbene complexes of Ni.701 In 2012, Shi and
4.3.1. Nickel. Catalysis by nickel complexes has been co-workers also obtained asymmetric sulfides in high yields by
known for a long time, but it has received special attention in using carbene complexes. The reactions with benzyl and
the 21st century after the successes of Pd and Cu catalysis. To aliphatic thiols proceeded with good yields (Scheme 195,
a large extent, “without reinventing the wheel”, scientists A).702
Nolan and co-workers demonstrated that nickel allyl
repeated the reactions performed earlier with palladium or
complexes with known carbene ligands were efficient catalysts
copper and obtained quite competitive results for nickel, but
for C(sp2)−S bond formation at low catalyst concentrations,
nickel catalysis has achieved particular success in cooperation with NHC = IPr*OMe showing the best result (Scheme 195,
with photoredox catalysts.697−699 B).703 A similar reaction was carried out with aromatic and
Of note, in 2008, Punniyamurthy and co-workers described aliphatic thiols and other carbene complexes (Scheme 195,
ligand-free nickel catalysis in the reaction of aryl halides with C).704
aromatic thiols, where aryl iodides reacted with excellent Nicasio, Prieto and co-workers have carried out cross-
yields.700 coupling reactions of a range of (hetero)aryl halides, including
Chem. Rev. 2022, 122, 16110−16293
Scheme 178
Scheme 179
aryl chlorides and aryl- and alkynyltosylates with aromatic and temperature571 and Ni(cod)2bpy or dppf at room temperature
aliphatic thiols. The nickel complex NiCl(allyl)- or 50 °C (57 examples of such a cross-coupling were
(PMe2terphenyl) was employed as a catalyst precursor in presented),185 and bidentate phosphine oxide ligands were
this reaction (Scheme 196, A).705 For chlorides and tosilates, also used.706 Arylation, alkenylation, and alkynylation of
especially with alkyl thiols, more harsh reaction conditions thioglycosides were carried out at room temperature.707
were used (for example, NMP 120 °C). The yields from good
Inter- and intramolecular thiolation under the action of thiols
to high levels were shown in the studied reactions (>50
products). Reaction selectivity was demonstrated on a number and their surrogates with the catalytic system Zn/NiCl2/Py/
of examples (Scheme 196, B). ethyl crotonate was carried out at room temperature.
To introduce a thiotrifluoromethyl group, the salt (±)-Chuangxinmycin was synthesized.708 Arylsulfonyl chlor-
(Me4N)+(SCF3−) was used with Ni(cod)2dmbpy at room ides were used in the reaction with aryl iodides in the presence
Chem. Rev. 2022, 122, 16110−16293
Scheme 180
Scheme 181
of Mn as a reducing agent and NiCl2·glyme as a catalyst (43 cycle includes the formation of the Ni−CN moiety and
examples of various diaryl (heteroaryl) sulfides).709 replacement of the CN group by SR.2
Schoenebeck and co-workers found conditions under which Upon using morpholin-4-ium morpholine-4-carbo-dithioate
a Ni(0)(cod) 2 complex with a ligand catalyzed the as a sulfur source, the Ni-catalyzed reaction of aryl halides (X =
trifluoromethylthiolation of aryl chlorides. The ligand was I, Br) results in the production of diaryl disulfides with yields
dppf�a bidentate phosphine ligand with a wide bite angle. For ranging from moderate for Br and Cl to high for I. However,
more problematic substrates, a small MeCN additive was with alkyl halides, disulfides were formed in good yields for
required (Scheme 197, A).710 The methodology was applied to both Br and Cl (Scheme 202).715
the synthesis of pharmaceuticals (Scheme 197, B). The following catalytic cycle was proposed in Figure 40.
Recently, Lipshutz and co-workers94 proposed conditions Formation of sulfides (diaryl and alkylaryl) using pyrrole-
under which a nickel-catalyzed reaction of aryl(heteroaryl)- based pincer Ni complexes was demonstrated. Of the three
halides (X = I, Br) with Ar(Het)SH proceeded in an aqueous complexes, the complex with R = Ph showed the best results.
solution in the presence of TPGS-750-M (DL-α-Tocopherol Upon replacing I with Br and Cl, the yield dropped to 44% and
methoxypolyethylene glycol succinate) in good to high yields 0%, respectively (Scheme 203).716
(Scheme 198). The obtained data suggest that the active catalyst is a Ni(I)
Of note, ca. 0.25 equiv of Zn could be used in the reaction. complex formed upon the reduction of Ni(II) with thiolate
By the example of the reaction of C10H21SH with p-
anions. Oxidative addition of ArI leads to the formation of a
iodofluorobenzene, it was shown that the catalyst could be
Ni(III) complex, in which the exchange of iodide for RS−
recycled, with a slight decrease in the yield in the fourth cycle
occurs, followed by reductive elimination and the formation of
(94 → 88%).
A comparison of bidentate phosphine and nitrogen- a product and regeneration of the Ni(I) complex.
containing ligands was carried out.711 Apparently, the proposed mechanism differs significantly
Stewart and co-workers demonstrated that the use of from that previously considered for S-cross-coupling with the
complexes of nickel with phosphite/phosphine ligands allowed participation of reduced nickel, where the catalytic cycle
the reaction of arylthiols with aryl(heteroaryl)chlorides with completely repeats the one known for Pd(0) catalysis.
both EWG and EDG to be carried out at 110 °C with An example of the identical behavior of PhM(PPh3)2Br (M
moderate to excellent yields (Scheme 199).712 A complex of = Ni or Pd) complexes in the reaction with R2S2, which was
nickel with a Schiff base (NiL2) catalyzed S-cross-coupling reduced to RS−, is presented in ref 717. The authors compared
with organochloride, including ArCl (Scheme 200).713 the catalytic activity of Pd−SCS and Ni−SNS pincer
Instead of traditionally used aryl halides (pseudo halides), complexes in the reaction of phenyl iodide with diphenyl
aryl nitriles were involved in the reaction. With the Ni(cod)2/ disulfide (Scheme 204).718
dcype (1,2-bis(dicyclohexylphosphino)ethane) catalyst in the Upon ordinary heating and microwave irradiation, the Ni
presence of KOtBu, the products were formed in good to high complex provided significantly better results than the Pd
yields. Interestingly, other ligands, including carbene ligands, complex. However, the opposite was observed for the Suzuki−
led to unsatisfactory results (Scheme 201).714 The catalytic Miyaura reaction.
Chem. Rev. 2022, 122, 16110−16293
Scheme 182
Scheme 183 substituent. The complex showed high activity and recycla-
bility in five cycles, with a yield drop from 86% to 80%. The
reaction was carried out in water under microwave irradiation
(Scheme 205).720
Aryl iodides with electron-donating substituents produce
high yields in the reaction with arylthioacetates catalyzed by
Ni(II)/bpy in the presence of Zn (Scheme 206, A).721 Aryl
iodides with p-NO2 or p-CN groups do not react.
The Ni2+/bpy Zn-catalyzed formation of diaryl sulfides using
phenyldithiocarbamates as a thiol surrogate is described
(Scheme 206, B).722
Upon studying the reactions of stable nickel aryl thiolate The cooperative action of the metal and the ligand allows
pincer complexes with bisphosphinite ligands with alkyl the S-cross-coupling reaction catalyzed by a complex of nickel
halides, Guan and co-workers concluded that the formation with a redox-active ligand to be carried out under mild
of ArSAlk proceeded via the SN2 mechanism or as a metathesis conditions (Scheme 207).723
of σ-bonds.719 Of note, in recent years, the method of electrocatalytic C−
Arylsulfonylhydrazides are widely used as sulfur sources. H/C−S-cross-coupling between electron-donor arenes and
They were applied in the reaction with aryl halides catalyzed heteroarenes with arylthiols, i.e., radical oxidative processes in
by the Ni complex with a Schiff base with an imidazolium the absence of an oxidizing agent,724,725 has been developed
Chem. Rev. 2022, 122, 16110−16293
Scheme 184
(see also the synthesis of benzothiazoles by the same Ni(II)-catalyzed synthesis of disulfides in the reaction of
authors726). Katritzky salts (alkyl 2,4,6-triphenylpyridinium) with diary-
The authors carried out electrochemical oxidative sulfona- ldisulfide and selenide was carried out (Scheme 211).733
tion of the CH bond using RSO2NHNH2 as a sulfonating Singh and co-workers carried out a nickel-catalyzed Chan−
agent (Scheme 208).727 Lam reaction with a large series of arylboronic acids with
Significant advances were observed upon applying electro- arylsulfonyl hydrazides under catalysis by NiCl2·6H2O/bpy
chemical synthesis728 and the combined action of electro- (DBU as a base, I2 as an oxidizing agent) (Scheme 212, A).734
chemistry and transition metal complexes (see ref 729 and Reactions with alkyl- and α-thienylboronic acids do not
references therein) in C−H functionalization. proceed. Thus, the authors proposed a convenient method for
Thiolation of aryl bromides and heteroaryl chlorides was the preparation of asymmetric thioesters.
carried out under nickel catalysis with electrochemical Recently, Hanaya and co-workers described a Ni(II)-
reduction at room temperature.730 The reaction proceeded mediated analogue of the Chan−Lam reaction between
arylboronic acids and thiols (Scheme 212, B).93
without a base and with an order of activity of aryl halides ArCl
S-Arylation of the cysteine fragment can be carried out
> ArBr, which was unusual for the Ullmann-type process
under the action of arylboronic acids with electron-with-
(Scheme 209, A).
drawing substituents (preferably with the NO2 group) at the
A large series of sulfides were obtained from aryl iodides
ortho position and the nickel salt Ni(OAc)2 as a catalyst
with various thiols (41 compounds) under catalysis by NiCl2· (Scheme 212, C).735
glyme (10 mol %) with different nitrogen-containing ligands, Ni-catalyzed sulfonylation of arylboronic acids was carried
of which dtbbpy demonstrated the best results under mild out under the action of Na2S2O5 in the presence of
electrochemical conditions with the participation of Ni(0), benzylammonium salts (Scheme 213).736 The reaction was
Ni(II), and Ni(III) complexes (Scheme 209, B).731 scaled, and 1.46 g (63%) of PhSO2Bn was obtained.
The use of electrochemical reduction in a Ni-catalyzed S- Nanocrystalline NiO−ZrO2 in a mesoporous material
cross-coupling reaction with alkyl and aryl bromides and the (MNZ-1) catalyzes S-cross-coupling in water at room
use of benzenethiosulfonates as the source of the RS group temperature (Scheme 214, A).737 The mixture of NiO and
allowed the production of a variety of sulfides in good to high ZrO2 itself is inactive. The catalyst loses its activity upon
yields (Scheme 210).732 recycling due to aggregation and leaching. The authors note
Chem. Rev. 2022, 122, 16110−16293
Scheme 189
Scheme 186
Figure 39. C−H functionalization in the sulfonylation reaction with

PhSO2Na.
Scheme 187 In a “green environment” (in water or polyethylene glycol),

a nickel ferrite (NiFe2O4NP)-catalyzed three-component
synthesis of diaryl sulfides was carried out. The reaction
proceeds in water upon using an inorganic base in the presence
of KF as a sulfur activator (Scheme 214, B).738 Of note,
chlorides react with high yield in this reaction.
Under similar conditions (NaOH, 80 °C), a Chan−Lam-
type reaction with arylboronic acid (22 examples, 65−96%)
that the reaction conditions are consistent with the principles was carried out, in which chlorides also reacted with high
of green chemistry. yields (with PhB(OH)2, I = 95%, Br = 95%, Cl = 85%). The
Chem. Rev. 2022, 122, 16110−16293
Scheme 190 only relatively low yield (65%) was observed in the reaction of
p-BrC6H4Cl (Br reacted) with p-Me-PhB(OH)2. Five cycles of
this reaction proceeded with practically no decrease in the
product yield (95% → 93%).
Both of the above-described reactions with aryl halides and
arylboronic acids were also successfully carried out for
nitroarenes in PEG200. For the reaction of p-nitroanisole,
catalyst recyclization was carried out, and it proceeded with a
loss of yield by the fifth cycle from 92% to 87%.738
A heterogeneous trimolecular reaction was carried out
between phenol esters and arylboronic acids in the presence of
sulfur with the participation of a NiFe2O4 nanocatalyst
(Scheme 214, C).739
Ph3SnCl can be used instead of phenylboronic acid. For
both reactions (with boronic acid and an organotin
compound), it was shown that the catalyst could be recycled:
it retained the activity in six cycles, after which the activity
dropped sharply.
A binuclear NiCo nanocatalyst on a polyvinylphenol
polymer soluble both in organic solvents and in water was
synthesized and used in cross-coupling (Scheme 214, D).740
The reaction did not proceed with the R1 acceptor group
(MeCO) and p-tolylthiol. Low yields were observed for
aliphatic thiol and p-ClC6H4SH with p-MeC6H4I, although the
same thiol reacted with p-MeOC6H4I in 92% yield.
Scheme 191
Chem. Rev. 2022, 122, 16110−16293
Scheme 192
Scheme 193
Scheme 194
The Ni catalyst (Ni on Co-CP coordination polymer) (Scheme 216, A).742 Diaryl selenides were formed in high
(Figure 41) catalyzed the reaction of aryl iodides with yields.
thiophenol and aliphatic thiols in high yields. No drop in the The heterogenized catalyst Fe3O4@SiO2@His@Ni(II) (His
yield was observed upon recycling (five cycles) (c-Hex-SH up = L-histidine) catalyzed the reaction of aryl/alkyl halides with
to 97%, Et-SH up to 94%) (Scheme 215).741 elemental sulfur, producing symmetric sulfides (Scheme 216,
A porous polymer material (CGP) formed via the reaction B).743
of cyanuric chloride with guanidine was used as a substrate for Formation of symmetric diaryl sulfides via the reaction of
NiNPs in the reactions of aryl halides with selenium powder aryl iodides with S8, catalyzed by a heterogenized Ni-
Chem. Rev. 2022, 122, 16110−16293
Scheme 195
process with S8 or thiourea. Under optimized conditions, both

sulfur sources produced high yields of symmetric sulfides not
only with PhI but also with PhBr and PhCl (Scheme 216,
D).745 The catalyst was used in five cycles with a small loss of
activity.
A convenient protocol for the synthesis of diaryl sulfides via
guanidine/MCM-41 catalyst, was studied (Scheme 216, C).744 the reaction of arylhydrazines with aromatic thiols catalyzed by
A slight decrease in the product yield is observed by the sixth nickel on a magnetic substrate was proposed. The reaction
cycle of recyclization. proceeded in water at room temperature, with N2 and H2O as
A heterogenized nickel complex on modified graphene oxide the only byproducts. The catalyst was easily separable and
was characterized and used as a catalyst in the Ullmann-type recyclable (seven cycles) (Scheme 217).86
Chem. Rev. 2022, 122, 16110−16293
Scheme 199
Scheme 200
Figure 40. Ni-catalyzed arylation of morpholin-4-ium morpholine-4-
carbo-dithioate.
Scheme 203
Scheme 201
Scheme 204
Thiolation of the C(sp2)−H bond of arenes catalyzed by

nickel was also carried out as a general cross-coupling and as an
S-cross-coupling along the path laid by Pd and Cu. Reactions
of C−H functionalization with the participation of directing
groups were studied: thiolation with disulfides with PIP as a
directing group under catalysis by NiCl2·6H2O/BINOL,746 reactions of an unactivated C(sp3)−H bond with disulfides and
NiCl2-catalyzed reaction with 8-aminoquinoline DG,747 direct the same DG,749,750 and sulfenylation of C(sp2)−H and
thiolation of the β-C(sp3)−H bond in aliphatic amides,748 C(sp3)−H bonds under catalysis by Ni(OTf)2 and DG.751
Chem. Rev. 2022, 122, 16110−16293
Scheme 205 phosphine complexes of nickel was used to functionalize the

C−H bond of arylamides with disulfides and, without
phosphine, with sulfonyl chlorides.754
Nishihara and co-workers synthesized benzoisoselenazolone
and its derivatives via direct selenylation of benzamides and
acrylamides with a directing group by elemental selenium in air
under Ni(OAc)2 catalysis (Scheme 218, A).755
Chalcogenation of anilines proceeds under the action of
dichalcogenides catalyzed by Ni(OTf)2 in the presence of the
oxidizing agent MnO2 and 2-pym as an easily removable DG
Scheme 206 (Scheme 218, B).756
An unusual formation of the C−S bond occurs when thiol
N-oxides act upon 1,2,3-triazole using NiSO4 as a catalyst
(Scheme 219).757 The proposed reaction mechanism allows
selectively thiolated 2-aryl-1,2,3-triazoles to be obtained in
good yields.
Interesting biologically active compounds are formed in a
nickel-catalyzed tandem reaction of 3-(2-hydroxyphenyl)-
acrylic acid with 2-iodobenzothiol (Scheme 220).758 In the
case of the bromo derivative, the reaction proceeded with
slightly lower yields (six examples, 52−75%).
For electron-rich indoles, thiolation to monosulfide
proceeded at position 3 under the action of S8 and catalysis
by Fe(NO3)3 or FeCl2 in the presence of KI. Under nickel
catalysis, the reaction with both sulfur and selenium proceeded
Scheme 207 with the formation of disulfide and diselenide (Scheme
221).759 The proposed mechanism involved the incorporation
of sulfur into the R2Ni(II) intermediate (Figure 42).
A combination of nickel and redox catalysis (ruthenium and
visible light) solves the issue of selective arylation of SH groups
containing unprotected peptides and complex biomolecules by
(hereroaryl)arylbromides (Figure 43).760
Scheme 208
Preparation of arylalkyl sulfides from alkanes and thiols was

carried out via a nickel-catalyzed oxidative reaction with the
ortho-CH thiolation of unactivated arenes with diaryldisulfides elimination of H2 (Scheme 222).761
under catalysis by NiCl2 in the presence of PhCO2H with the 4.3.2. Cobalt. The S-cross-coupling of aryl iodides
PIP directing group752 or by Ni(OTf)2 in the presence of (bromides) with aromatic and aliphatic thiols, catalyzed by
LiOtBu and thiolation and selenylation directed by N-benzoyl CoI2(dppe)/Zn and pyridine as a base, proceeds with excellent
α-amino acid derivatives753 were studied. Catalysis by yield under mild conditions (Scheme 223, A).762
Chem. Rev. 2022, 122, 16110−16293
Scheme 209
Scheme 210
Tsai and co-workers demonstrated that CoCl2·6H2O with a As in the case of Ni-catalyzed Ullmann-type processes,
ligand (L) perfectly catalyzed the reaction of aryl halides with reactions for the preparation of asymmetric sulfides were
thiols in water (Scheme 223, B). In the reaction of acyl iodide carried out using Co catalysts with the participation of
with thiophenol, the aqueous catalytic system was recycled nitrobenzenes. The reaction was carried out using magnetic
seven times with a decrease in the activity (99% → 60%).763 CoFe2O4 with the participation of nitrobenzenes with electron-
Chem. Rev. 2022, 122, 16110−16293
Scheme 211
Scheme 212
withdrawing and electron-donating substituents and bromo- Co catalyzes S(Se)-cross-coupling involving NaSCN (or
and chlorobenzyl derivatives (Scheme 224, 20 examples, 50− KSeCN) and C−H functionalization, producing benzo[b]thio-
91%, 5 mol % of cat., KOAc, DMSO, 80 °C). The catalyst was (selenophene)-fused imidazo[1,2-a]pyridines. The sequence of
recycled ten times without a noticeable loss of activity.764
stages can vary (Scheme 226).766
Co(II) immobilized on an aminated MOF was used in the
By the example of the reaction of an organozinc compound
reaction of arylhalogenides with aromatic thiols (Scheme
225).765 The yields were comparable to those given in the with diaryl disulfide (Chan−Lam-type reaction), Knochel and
literature for other heterogeneous catalysts. The catalyst co-workers studied the catalytic action of Fe, Pd, Cu, Ni, and
retained its activity in seven cycles. Co salts with various anions (THF, rt, 12 h, 10 mol % cat.).
Chem. Rev. 2022, 122, 16110−16293
Scheme 213
Scheme 214
Figure 41. Structure of Ni on Co-CP.
Chem. Rev. 2022, 122, 16110−16293
Scheme 215 for such a reaction (Scheme 229, A).768 A radical reaction
mechanism was assumed. C(sp2)−H thiolation of indoles with
an N-pym directing group proceeds selectively at position C-2
(Scheme 229, B).769
In 2018, Wang and Li carried out direct thiolation of
aromatic amides with disulfides under CoBr2/DTBP catalysis
The best results were obtained for CoCl2 (95%, for R1 = H, R2 (Scheme 230, (1)).770 For a large number of examples (27
= p-OMe) (Scheme 227).90 compounds), the reaction was carried out with yields ranging
Various types of reactions involving the direct introduction from moderate to good and even high (33−93%). A possible
of a thiol group into arenes�C(sp2)−H bond functionaliza- radical mechanism is shown in Figure 44. The method was
tion�catalyzed by various cobalt derivatives are known. applied to the synthesis of quetiapine (Scheme 230, (2)).
An efficient technique for the thiolation of electron-enriched Co(acac)3 catalyzes the monoselective methylthiolation of
arenes (heteroarenes) was proposed in ref 767. The reaction benzamides by DMSO in the presence of an oxidizing agent
with a water-soluble Co(II) phthalocyanine complex was and an activating agent (PhCOCl). DMSO and PhCOCl
carried out under mild conditions using O2 as an oxidizing supposedly form the intermediate Me2S+−O−C(O)Ph that
agent. In all cases with arylthiols, the products were obtained in promotes deprotonation, although the exact mechanism has
high yields (Scheme 228). not yet been established (Scheme 231).771
A Co(II)-catalyzed thiolation of arenes by elemental sulfur, The authors772,773 carried out functionalization of the
with 8-aminoquinolium as a directing group, was studied to C(sp2)−H bond in phenols and naphthols with DG resulting
obtain symmetric diaryl sulfides in yields that were moderate from acylation of the hydroxyl group catalyzed by homoge-
Scheme 216
Chem. Rev. 2022, 122, 16110−16293
Scheme 217
Scheme 218
neous and heterogeneous CoCl2 complexes. In the heteroge- The heterogeneous cobalt phthalocyanine catalyst on a
neous version, the complex was bound to the magnetic support magnetic support of Fe3O4 coated with two hydroxides of Mg-
Fe3O4SiO2−UT@CoII (Scheme 232). Recycling of the catalyst
proceeded with a gradual drop in the yield from 91% to 71% and Al-CoPcS/MgAl-LDH@Fe3O4 demonstrated excellent
by the fifth cycle. results in the oxidation of thiols by oxygen.774
Chem. Rev. 2022, 122, 16110−16293
Scheme 219
Scheme 220
Scheme 221
S-cross-coupling reactions with aryl iodides and aryl and alkyl

thiols catalyzed by FeCl3 with various ligands are described:
DMEDA (NaOtBu or Cs2CO3, K3PO4, toluene, 135 °C, 24 h,
18 examples, 32−98%);777 BINAP or XantPhos (KOtBu or
Cs2CO3, toluene or dioxane, 135 °C, 24 h, 24 examples, 62−
99%);778 and 4,4′-bis(trimethylammoniummethyl)-2,2′-bipyr-
idyl dibromide (KOH, water, reflux, 24 h, air).779
The reaction of arylboronic acid with diaryl and dialkyl
dichalcogenides (Se, Te) catalyzed by iron powder in DMSO
Unusual CH thiolation with the formation of H2 without an was carried out (130 °C, 20 h, Se: 18 examples (62−97%), Te:
oxidant under the action of visible light and catalysis by cobalt five examples (86−98%)).780
complexes was described by Lei, Wu, and co-workers.775 Upon In 2012, Lee reported a reaction of vinyl halides (I, Br, Cl)
optimization using four cobalt complexes and various bases, with thiols with excellent yields of vinyl sulfides in the reaction
the conditions were found, under which thiobenzanilide was of iodides (FeCl3/Xantphos, Scheme 234, A).781 However, in
selectively converted to 2-aryl(alkyl)benzothiazole in good to the case of bromides and chlorides, the yields were much lower
excellent yields (Scheme 233). (Br: up to 74%, Cl: up to 62%).
The following reaction mechanism was proposed in Figure A “green methodology” was proposed for the production of
45. arylated aromatic and aliphatic thiols, and it included the use of
4.3.3. Iron. The catalytic properties of iron in oxidative a FeCl3−L-proline catalytic system in water. The technique, as
reactions were known more than 100 years ago;776 however, its the authors pointed out, was applicable to a wide range of
involvement in cross-coupling reactions with the formation of substrates. However, high yields of the product could be
the C(sp2)−S bond has begun to be studied relatively recently. obtained only for aryl iodides containing electron-withdrawing
Chem. Rev. 2022, 122, 16110−16293
Scheme 222
Scheme 223
Scheme 224
Scheme 225
substituents (Scheme 234, B).782 The yield decreased upon In the reaction of diaryl iodonium salts (cyclic and linear)
changing from iodides to bromides and chlorides, as well as with sodium sulfide catalyzed by FeCl3 without a ligand in
upon introducing donor substituents into thiophenol. DMSO, the corresponding diaryl sulfides are formed in good
Chem. Rev. 2022, 122, 16110−16293
Scheme 228
Figure 42. Ni catalysis of the reaction of indole with molecular S.
Scheme 229
Figure 43. Ni and Ru complexes used in redox catalysis.
Scheme 226
Scheme 230
Scheme 227
cross-coupling of diiodoarenes with aromatic thiols, yielding

yields (Scheme 234, C).783 However, the yield of linear dithioarenes (Scheme 234, D).330
sulfides is much lower than that of cyclic sulfides. Another bimetallic catalytic system (FeCl2·4H2O/CuO) was
Catalysis by an FeCl3/CuI bimetallic system in DMSO used to introduce the RS group into 6-iodoimidazo[1,2-
without additional ligands produced excellent results in the a]pyridine (Scheme 235, A).470 The reaction proceeds with
Chem. Rev. 2022, 122, 16110−16293
Figure 44. Radical mechanism for CH-thiolation with DG catalyzed

by Co(II).
Scheme 231
Figure 45. Ru/Co catalysis in 2-phenylthiazole synthesis.
Scheme 234
Scheme 232
Scheme 233
Chem. Rev. 2022, 122, 16110−16293
Scheme 238
Scheme 235
in this reaction is the key compound responsible for the

selectivity of the coupling.
A one-pot synthesis of fused azo[2,1-b][1,3]-benzothiazi-
nones in a cascade process involving S-cross-coupling and
high yields (>70%) for aromatic and heteroaromatic thiols and FeCl3-catalyzed cyclization was described (Scheme 238, B).788
with moderate to good yields for aliphatic thiols, including Of note, the ligands commonly used for iron reduce the yield
benzylthiol. of the reaction product in this case.
Fe(II) catalyzes the cross-coupling of ortho-iodoanilines with Under catalysis by FeCl3/L, benzothiazoles are arylated with
benzylthiols with simultaneous amination at the C(sp3)−H aryl iodides in the presence of alkali in water with ring opening
bond (Scheme 235, B).784 The reaction with bromides and the formation of aryl(2-aminoaryl) sulfides (Scheme
proceeds with a slight decrease in the yield. 239).789 Of note, the reaction is of interest since the 2-
Cross-coupling with the formation of C−Se and C−Te
bonds was carried out in the reaction of ArHal with Se(0) and Scheme 239
Te(0) using the heterogeneous catalyst nano-Fe3O4 on
graphene oxide (Scheme 236).785 The reaction with bromides
Scheme 236
aminothiophenol fragment is found in many pharmaceutical

and biologically active compounds.
and chlorides proceeds with lower yields (R = Ph, I (98%) > The preparation of alkynylaryl selenides catalyzed by
Br (73%) > Cl (60%)). The catalyst retains its activity for four Fe 3 O 4 NPs on activated carbon was carried out via
cycles. mechanochemical synthesis (solid-state grinding) of alkynes
Ranu and co-workers demonstrated that a diazonium salt with diselenides (Scheme 240, A).790 The magnetic catalyst
formed in situ in the reaction of aryl(heteroaryl)anilines with retains its activity in five cycles with a slight decrease in the
diselenides, ditellurides, and disulfides, mediated by Fe(0)NPs product yield.
(1 equiv), under oxidizing conditions, leads to the formation of A hollow nanoshell sphere, a magnetically recoverable
catalyst Fe@Fe/Pd, was proposed to be used in the reaction
Scheme 237 of C(sp)−S bond formation carried out with the participation
of (RS)2 or RSH in water (Scheme 240, B).791
High yields were obtained when using Ar with electron-
donating groups (p-Me, 98%; p-OMe, 89%), and low yields
were obtained when using Ar with electron-withdrawing
groups (p-Br and p-Cl, 35% and 20%, respectively). However,
in 40−45 min, the yields increased to 86% and 74%,
respectively.
A similar reaction of dichalcogenides (Se, Te) with terminal
asymmetric diaryl (heteroaryl) selenides and diaryl tellurides in acetylenes is catalyzed by magnetite (Fe3O4) NPs. The catalyst
good yields (Scheme 237).786 A radical reaction mechanism can be recycled but with a gradual drop in the yield (91% →
was proposed. 80% by the fourth cycle) (Scheme 240, C).792
Of particular interest is the ability of iron salts to catalyze C−H activation of electron-donor indole under the action of
oxidative C−H functionalization under mild conditions. sulfur (selenium) and in excess FeSO4·7H2O led to the
Intramolecular cyclization producing benzothiazoles can be unexpected production of 3,3-bisindolyl thioether (selenide);
seen as an example (Scheme 238, A).787 In addition to the the addition of I2 and O2 could make the reaction catalytic
requirement of using an oxidizing agent, the presence of (Scheme 241, A).759
pyridine is essential. The reaction is radical, and the yield FeCl3 in the presence of KI effectively catalyzed the reaction
decreases dramatically upon the addition of TEMPO. Pyridine of indole with R2Se2 in DMSO. Under mild conditions, the
Chem. Rev. 2022, 122, 16110−16293
The chalcogenation reaction initiated by I2 and catalyzed by

FeF3 was carried out with arylamines797 and indoles798
(Scheme 242, C (1) and (2)). The interaction between
indoles and thiols under FeCl3 catalysis was described.799
Scheme 241 Fe-based MOFs catalyze the oxidative condensation of
alcohols with o-aminothiophenols when exposed to visible light
using O2 as an oxidizing agent to produce substituted
Scheme 243
reaction proceeded at position 3 for unsubstituted indole or

Me- or Bn-N-substituted indoles with high yields. For the N-
COMe derivative, the reaction did not proceed. In the
presence of a substituent at position 3, selenylation occurred
at position 2 (Scheme 241, B).793 With disulfide, the yields
were somewhat lower, although still rather high (8 examples,
72−96%).
Xu and co-workers794 described a FeCl3/DBU-catalyzed
direct reaction of benzoselenoles with the C(sp2)−H bond of
indole, which resulted in biologically active 2-benzenesele- benzothiazoles (Scheme 243, A).800 In three cycles, the yield
nonyl-1H-indoles (Scheme 241, C). remained the same.
The reaction with pyrrole proceeded in a similar way (9 Alkylaryl sulfides and selenides can be synthesized via a
examples, 59−79%). It supposedly involved an intermediate in rather exotic method: upon the action of a diaryldichalcoge-
which Fe(III) coordinated two hydrogen atoms NH···Fe···H− nide on cycloalkyl hydroperoxide catalyzed by iron. The
C (2nd position in indole). reaction proceeds as a redox-neutral process with the cleavage
Upon using a stoichiometric quantity of FeCl3, direct of the C−C bond, resulting in a keto-functionalized thioester
sulfenylation and selenylation of phenols under the action of (Scheme 243, B).801
diphenyl disulfides or diselenides in the presence of oxygen An Fe(III)-catalyzed sulfonylation of quinoline N-oxides
proceeded with high yields (Scheme 242, A).795 with sodium sulfinate was described and proceeded similarly to
It was shown that CH-thiolation of electron-rich 1,3,5- the reactions catalyzed by CuBr2691 or I2802,803 (Scheme 243,
trimethoxybenzene could proceed under the action of C). A radical reaction mechanism was assumed.804
disulfides using an iron salt as a cheap catalyst (Scheme 242, Lee and co-workers proposed a novel reaction for the
B).796 With indole and N-methylindole, the yields were 44% synthesis of esters from aldehydes catalyzed by FeBr2 in the
and 41%, respectively. presence of TBHP, and 41 compounds were obtained in
Chem. Rev. 2022, 122, 16110−16293
Scheme 245
Figure 46. Fe(II)-catalyzed thioester formation from aldehydes.
moderate to good yields (Scheme 243, D).805 A radical

mechanism was proposed (Figure 46).
4.3.4. Ruthenium. Ruthenium-catalyzed reactions play a
significant role in organic synthesis.806
An example of a cross-coupling reaction catalyzed by
ruthenium is the reaction of alkenyl triflates with zinc thiolates
Scheme 244
formed in situ in the reaction of zinc with disulfides (Scheme

244).807
Direct C(sp2)−H selenylation of arenes catalyzed by Ru(II)
was carried out with the electrophilic reagent PhSeCl using Scheme 246
pyrazole as DG (Scheme 245, A).808 Under the same
conditions, with Py as DG, the yields were lower (12 examples,
45−78%), and for pyrimidine (R3 = 2-Me), the yield was 30%.
Ortho-thiolation and selenylation under the action of R2Y2
(Y = S, Se) upon Ru(II) catalysis under the optimized
conditions were selective (Scheme 245, B).809 Selenylation of
aryl acetic amides and esters upon weak coordination of DG
with Ru proceeds in a similar manner (Scheme 245, C).810
Efficient Ru-catalyzed C−H selenylation of benzamides was
described (Scheme 245, D).811
An example of remote sulfonylation in the Ru-catalyzed
reaction of N-aryl-2-aminopyridines into the pyridine ring is
demonstrated in ref 812 (Scheme 246, A).
Another example of Ru(II)-catalyzed sulfonylations with Py Scheme 247
as a directing group was described by Frost and co-workers.
The reaction proceeds at the meta position, and sulfones are
obtained in moderate to good yields (Scheme 246, B).296 The
explanation of the observed regioselectivity is related to the
formation of a complex in which Ru does not participate
directly in the reaction of sulfonyl chloride but orientates its
entry into the para-position of the complex.
Mechanistic insight into meta-sulfonation catalyzed by
ruthenium is discussed in ref 813.
The chalcogenation of benzoic acid and heteroaromatic
acids, catalyzed by Ru(II), proceeds as di- or monosubstitution
(with the ortho-position occupied) due to the weak Ru(II) is able to activate the C−H bond in maleimides for
coordination of Ru with oxygen (Scheme 247, A).814 electrophilic attack by Ph2Se2 (Scheme 247, B).815 Under
TEMPO and other scavengers have no impact on the reaction these conditions, yields with Ph2S2 are moderate. The authors
route. note that maleimide reacts as an electrophile. This is a new
Chem. Rev. 2022, 122, 16110−16293
example of such a Ru-catalyzed reaction with maleimide and of Scheme 249

a direct selenylation of alkenes in general.
A heterogeneous variant of the indole selenylation reaction
under the action of Ph2Se2 was carried out. The Ru/RuOx
system has a synergistic effect, the magnitude of which
depends on the Ru(0)/RuOx ratio. The indole selenylation
Scheme 248
reaction proceeds under optimized conditions with almost

quantitative yields at room temperature (Scheme 248, A).816
Indoles substituted at the benzene ring reacted with high
yields, and indole also reacted with Bn2Se2. However,
benzofuran and benzothiophene were inactive. The reaction
of indole with Ph2S2 proceeded with a 12% yield. Thus, Ph2Se2
Figure 48. Mechanism of the photocatalytic reaction of C−H
demonstrated the highest activity, and it reacted with electron- functionalization with Ru complexes leading to substituted
donating β-naphthol and β-aminonaphthalene in excellent benzothiazoles.
yields (98% and 93%, respectively).
The use of solar energy in chemical processes is the most
The use of visible light allowed for the first time to carry out
important direction, to which considerable attention has been
Ru-catalyzed methylsulfoxidation in the reaction of DMSO as a
recently paid. These studies include photoredox reactions
sulfur source with aryl diazonium salts (Scheme 250, A).835
under the action of visible light in which polypyridine
complexes of Ru (or Ir) with photocatalytic properties act as
photosensitizers.817−832 Scheme 250
Zheng and co-workers carried out a photoredox reaction
(visible light, Ru(bpy)3Cl2) of N-methylindole with arylsul-
fonyl chlorides (Scheme 248, B).833 The introduction of
substituents into the benzene ring of indole did not affect the
product yield, while the replacement of N-Me by other groups
Figure 47. Photoredox reaction between indole and arylsulfonyl

chloride, mediated by Ru. C−S bond formation from redox-active esters was demon-
strated in the Ru-catalyzed reaction with disulfides (Scheme
250, B).836
4.3.5. Iridium. When considering S-cross-coupling reac-
reduced the yield and even completely inhibited the reaction tions catalyzed by transition metal complexes, we mentioned
(N-Boc). The catalytic cycle is shown below (Figure 47). that visible-light irradiation improved the process and, in the
Cheng and co-workers used the photocatalytic properties of presence of a photoactive compound (photosensitizer),
a Ru(II) bispyridyl complex in the C−H functionalization initiated the reaction. In 2017, Fu and co-workers broke the
reaction in the synthesis of substituted benzothiazoles from news in the paper titled “Room-temperature arylation of thiols:
ortho-thioanilides under visible-light irradiation (Scheme breakthrough with aryl chlorides”. They carried out the
249).834 The reaction mechanism is proposed in Figure 48. reactions of thiols with various aryl halides (including ArCl)
Chem. Rev. 2022, 122, 16110−16293
that proceeded with high yields at rt under visible-light Scheme 252

irradiation in the presence of iridium complexes, of which [fac-
Scheme 251
Figure 49. Photoredox reaction between arylhalides and thiols

catalyzed by Ir(III). Figure 50. Photoredox process (Ir(III)) in the synthesis of sulfones.
Scheme 253
837
Ir(ppy)3] was the best (Scheme 251). A mechanism of the
photoredox arylation of thiols was proposed (Figure 49).
Another example of a sulfonylation reaction producing 4-
(sulfonylmethyl)isoquinoline-1,3(2H,4H)-diones, promoted
by visible light with the participation of iridium, is given in
ref 838.
Speaking about sulfonylation, the work of a large team of
authors on the sulfonylation of anilines mediated by visible
light should be mentioned. In this process, an iridium cationic
complex demonstrated the highest efficiency as a redox catalyst
(Scheme 252).839 A large family of sulfones (44 examples)
were obtained in moderate to good yields by using this
method. A catalytic cycle of the reaction was proposed (Figure
50).
Photoredox reactions involving iridium or ruthenium
complexes allowed the reaction of heterocycles with ArSO2Cl
to produce a sulfonylation product at room temperature or an PPh3 complex (toluene, NaOtBu, 100 °C, 24 h), with good to
arylation product at a higher temperature (Scheme 253, A, high yields (55−99%, 25 examples).843
Figure 51).840 Such reaction with aryl bromides and chlorides was
A photoredox reaction catalyzed by an iridium complex successfully carried out under catalysis by the (POCOP)Rh-
under the action of visible light leads to the functionalization of (H)(Cl) pincer complex in which Rh(I)/Rh(III) complexes
CH-amides in the reaction with RSO2Cl, producing β- were involved.844
amidovinyl sulfones in good to high yields (Scheme 253, B).841 A rhodium-catalyzed thiolation reaction also proceeded
An iridium complex (photocatalyst [Ir(dF(CF 3 )- when using disulfides and other sulfur sources.845 Thiolation of
ppy)2(dtbbpy)](PF6)) and visible light promote the reaction polychloroalkanes was carried out using a heterogeneous
of aliphatic carboxylic acids with (trifluoromethylthio)- Rh(I)−MCM-41−2P-RhCl(PPh3) complex.846 The reaction
phthalimide, producing AlkSCF3.842 with arylboronic acids is also known for rhodium complexes87
4.3.6. Rhodium. Cross-coupling with the formation of (Scheme 254).
diaryl sulfides proceeds in the reaction of aryl iodides with Rhodium-catalyzed C−H functionalization involves surro-
aromatic and aliphatic thiols catalyzed by the [RhCl(cod)]2/ gates. Thus, thiolation of substituted benzoxazole and
Chem. Rev. 2022, 122, 16110−16293
Figure 51. Photoredox sulfonylation of heterocycles at room temperature.
Scheme 254 Rh-catalyzed electrophilic phenylselenation of quinone and

benzoquinone under the action of N-(phenylseleno)-
phthalimide proceeded with good yields (Scheme 257).853
A combination of C−H activation and hypervalent iodine
chemistry catalyzed by a rhodium complex (Rh(III)) was
studied. At the first stage of this one-pot process, Rh-catalyzed
hyperiodination proceeded, followed by an uncatalyzed
sulfonylation reaction. The exchange with PhSNa proceeded
benzothiazole under the action of 2-(phenylthio)- similarly. The reaction with NaSCN at the second stage
isobutyrophenone as a donor of phenylthio groups proceeds required catalysis by Cu(OTf)2 (Scheme 258).854
under catalysis by a complex of rhodium hydride and dimethyl Rh(III)-catalyzed thiolation of the vinyl atom in C(sp2)−H
disulfide (Scheme 255).847 in N-tosylacrylamide was successfully carried out, allowing us
An extensive study on the reaction of unactivated arenes to obtain (Z)-β-alkenyl sulfides (Scheme 259).855 The use of
with a directing group for both sulfur848 and selenium849 was the 2-PyO or 2-Py-NH fragment as a directing group allows
carried out. Catalysis with the participation of [RhCp*Cl2]2 in selective ortho-chalcogenation of phenols and anilines856
the presence of AgOTf and Cu(OAc)2 was used for arenes and (Scheme 260, A). Efficient C−H thiolation and selenylation
heteroarenes containing different directing groups (Scheme with a directing group catalyzed by a rhodium complex in a
256, A).848 The selenylation reaction was carried out under the
[bmim]OTf medium under the action of disulfides and
action of diselenide or phenylselenyl chloride. The following
diselenides was described (Scheme 260, B).857
catalytic cycle was proposed (Figure 52).
Rh(III)-catalyzed thiolation of azobenzenes (Scheme 256, B Thiolation of indole by the electrophilic SCF3 group,
(1)) and aromatic ketazines (Scheme 256, B (2)) was carried catalyzed by Rh(III) in the presence of N-pyridine, proceeds
out.850,851 The authors showed that Rh(III)-catalyzed CH- at position 2 (Scheme 261, A).858 Similarly, in the presence of
thiolation proceeded easily even with weakly coordinating DG DG at the nitrogen in the indole, selenylation to position 2 of
if a suitable ligand was present (Scheme 256, C).852 In the case the indole occurs under the action of a specially obtained
of PhSSPh, 33 compounds, including heteroaryl derivatives, selenating agent, benzoselenazolone (Scheme 261, B).859 The
were obtained, predominantly in high yields. reaction was applied to introduce Se into DNA.
Scheme 255
Chem. Rev. 2022, 122, 16110−16293
Scheme 256
Chalcogenation of indole with DG using the same Rh/Ag/ sulfides in good yields under mild conditions (Scheme 263,
Cu catalytic system proceeds, depending on the substituent at A).862
position 2, at position 4 (R2 = H), or with the activation of the A similar work, in which a silver salt was used in catalytic
C(sp3)−H bond at R2 = Me (Scheme 262, A).860 Thiolation amounts in the presence of the oxidizing agent Cu(OAc)2·
H2O, was carried out for the reaction of α-methoxynaph-
and selenylation of indolines with a pyrimidyl directing group
thalene with R2S2 (up to 95%) and R2Se2 (up to 87%), as well
under catalysis by a Rh(III) complex occur at position 7 as 1,3,5-trimethoxybenzene (73%) and mesitylene (64%) (15%
(Scheme 262, B).861 AgSbF6, 0.4−1.0 equiv of Cu(OAc)2·H2O, DCE, 100 °C, 12 h;
4.3.7. Silver. A AgNO3-mediated reaction of electron-rich R = (p-ClC6H4)2Y2).863
aromatic compounds with aromatic (heteroaromatic) disul- AgI-mediated CH-sulfonation of cyclic enamides was
fides leads to the production of aromatic and heteroaromatic described (Scheme 263, B).864 Upon AgI-catalyzed selenyla-
Chem. Rev. 2022, 122, 16110−16293
Scheme 260
Figure 52. Rh-catalyzed CH → CS transformation with DG. Scheme 261
Scheme 257
interest, was also studied.865 The proposed methodology was a

direct continuation of the work of Ackermann and co-workers,
who used a large amount of silver salts (Scheme 263, D).866 In
the case of R4 = Alk, the reaction did not proceed, and the
Scheme 258
product was also not formed in the case of R4 = p-OHC6H4 or
p-NH2C6H4.
Selenization of terminal acetylenes was carried out by the
action of diaryldiselenides under AgNO3 catalysis at room
temperature with high yields (Scheme 264).867
Decarboxylation of alkyl carboxylic acids in the presence of
Ar2S2 under the action of Ag(I) and the oxidizing agent
K2S2O8 leads to the formation of alkylaryl sulfides (Scheme
265, A (1)).868 A radical mechanism is supposed for the
Scheme 259 reaction (Scheme 265, A (2)).
The AgNO3-catalyzed reaction of diselenides with arylbor-
onic acids, being a direct analogue of the Chan−Lam reaction,
allows diaryl- and alkylaryl sulfides to be obtained in good to
high yields (10 mol % of AgNO3, 1,4-dioxane, 100 °C, 6 h, air,
21 examples, 55−96%). The participation of Ag(III) in the
catalytic cycle is assumed.869
A silver salt mediated a Chan−Lam-type reaction, the
products of which were formed in high yields, albeit at a high
temperature (Scheme 265, B).870 Liu, Zhou, and co-workers
tion of 3-substituted indole, remote selenylation at position 5 described the production of selenium heterocycles via radical
occurs (Scheme 263, C).112 cyclization in the reaction of arylboronic acids with elemental
DABCO-catalyzed and Ag(I)-promoted thiolation of pyr- selenium, catalyzed by AgNO3 in the presence of an oxidizing
azolones, the products of which were of pharmaceutical agent (Scheme 265, C).871
Chem. Rev. 2022, 122, 16110−16293
Scheme 262
Scheme 263
4.3.8. Molybdenum. Bimetallic BaMoO4 nanoparticles are good yields under rather mild conditions (Scheme 268, A).874
capable of catalyzing S-cross-coupling involving thiols with The authors noted that the six tested ligands did not affect the
good to high yields (Scheme 266).872 reaction. With bromides, the yield dropped sharply. (Z)-Ethyl
Formation of the C(sp2)−S bond was observed under the 3-iodoacrylate did not react.
action of various oxidizing systems, including metal salts. An Lee and co-workers demonstrated that manganese could
example is the reaction of electron-rich arenes with also catalyze the S-cross-coupling of aryl iodides with thiols in
dichalcogenides under the action of MoCl5 (Scheme 267).873 good to excellent yields (Scheme 268, B).875 The reaction was
4.3.9. Manganese. In 2010, it was shown that MnCl2· scaleable. There is a known reaction of sulfonation of N-
4H2O without ligands could catalyze the reactions of aryl and methylamides with arenesylfonyl hydrazides catalyzed by
styryl iodides with aromatic and aliphatic thiols in DMSO with Mn(OAc)2 in the presence of peroxide (Scheme 268, C).876
Chem. Rev. 2022, 122, 16110−16293
Scheme 264
Scheme 265
Chem. Rev. 2022, 122, 16110−16293
Scheme 267
Scheme 268
Scheme 270
of the C(sp2)−S bond (Scheme 270, A).883 Another

representative lanthanide oxide, [Ce(L-Pro)2]2Ox, showed
high efficiency in the reaction of p-NO2C6H4I with electron-
4.3.10. Zirconium, Bismuth, and Indium. Peptide donor arylthiols (Scheme 270, B).884 This compound
nanofibers decorated with zirconium oxide NPs proved to be (dapsone precursor) was obtained in gram quantities (83%).
an efficient catalyst for the preparation of symmetric sulfides by The recycling potential of the reaction with PhSH was studied:
using elemental sulfur and 2-thiobarbituric acid (Scheme 269, in five cycles, the yield dropped from >99% to 76%.
A).877 4.4. Photoredox Initiation of Reactions Catalyzed by
A zirconium oxide complex anchored on boehmite NPs was Transition Metal Complexes
recycled five times without a noticeable loss of catalytic activity Regarding the revolutionary transformations in the field of
(Scheme 269, B).878 The reaction of aryl halides (X = I, Br) cross-coupling by the example of thioetherification, the
with variously substituted aryl thiols, but without strong transition from palladium catalysis to copper catalysis; the
electron-withdrawing groups, proceeds with good to high use of arylboronic acids or CH-activation, which allowed
yields upon using bismuth(III) oxide in water as a catalyst simplifying this reaction and reducing its cost; and finally the
(Scheme 269, C).879 use of heterogeneous and nanocatalysts capable of regener-
Salts and oxides of indium(III) can catalyze S-cross-coupling ation, we should consider, at least briefly, a new stage in the
reactions. Several examples are provided below. Indium- application of photochemistry in organic synthesis and a new
catalyzed cross-coupling of aryl iodides with aromatic and stage in the application of radical chemistry to the processes of
aliphatic thiols was carried out (Scheme 269, D).880 Indium the formation of C−C and C−heteroatom bonds. Photo-
nano-oxide In2O3 also perfectly catalyzed this reaction in the chemical processes and photoredox catalysis with the
absence of a ligand. The catalyst could be recycled (Scheme involvement of sulfur species are a large actively developing
269, E).881 An InI3-catalyzed conversion of benzyl alcohol to area. In this review, we are not able to consider it in detail, and
dibenzyl sulfide or selenide under the action of molecular we only focus on some representative studies related to the
sulfur or selenium in the presence of triethylsilane was subject topic.
described.882 In S-cross-coupling reactions, an excellent example of such
4.3.11. Lanthanides. Nageswar and co-workers used double catalysis is the reaction in which visible light initiates
lanthanum oxide as a heterogeneous catalyst for the formation electron transfer with the participation of photosensitizers
Chem. Rev. 2022, 122, 16110−16293
responsible for the single electron transfer (SET) step and the Scheme 272
formation of thiyl radicals. These reactions are characterized by
mild conditions, and they allow for carrying out cross-coupling
reactions with C(sp3)-hybridized radicals. Here is an example
from the work by Molander and co-workers,885,886 who used
alkylbis(catecholato)silicates as precursors of a radical because
they had the required oxidative potential (Scheme 271, A).
Using a diisopropyl derivative of silicate as a proton acceptor, a
Scheme 271
Figure 54. Photoredox catalysis by Ni and Ir in sulfide synthesis.
Scheme 273
Figure 53. Double catalysis by Ni and Ru in the synthesis of sulfides.
series of sulfides were obtained in the reaction of p-

bromobenzonitrile with various thiols (Scheme 271, B).
The possible mechanism is shown in Figure 53.
A photoredox-mediated, Ir-photocatalyzed reaction of aryl
and heteryl iodides with thiols (aromatic, benzyl, and alkyl)
catalyzed by nickel was studied by Johannes, Oderinde, and co-
workers (Scheme 272).887 The reaction is catalyzed by Ni(I).
A mechanism involving thiyl radicals was proposed (Figure
54). Thus, thiyl radicals of various types allow selectively
obtaining the products of S-cross-coupling.
In a recently published article,888 a dual Ni/Ir catalyst was the catalytic cycle was proposed.889 The role of the pyridinium
employed in the reaction of heteroaromatic bromides with α- iodide salt formed during the reaction was pointed out.
thioacetic acid (as a source of sulfur), and various Understanding the reaction pathways and gaining insight into
heteroaromatic sulfides were obtained as products in good to the nature of plausible intermediates made it possible to
high yields (Scheme 273, A). The involvement of a free radical improve the yield in the reaction between aryl bromides and p-
mechanism with the participation of thiyl radicals was MeO-benzyl thiol. In the text above, a similar work was
suggested for the reaction. discussed with the participation of the Ru complex.760
The reaction mechanism was studied in detail by Nocera A combination of photoredox catalysis with catalysis by
and co-workers, and the participation of Ni(I) and Ni(III) in transition metal complexes, carried out by Lin and co-workers
Chem. Rev. 2022, 122, 16110−16293
in MOFs (Zr12-Ir-Ni) under visible-light irradiation, gives 5.1. Palladium-Catalyzed Transformations

significant advantages over a similar homogeneous reaction Employing very common Pd(OAc)2 as a catalyst precursor, a
due to many factors, such as stabilization of the photoredox complex mechanistic study of Z−H bond addition to alkynes
catalyst and an increase in local catalyst concentration. (Scheme 274) was carried out using experimental methods and
computational modeling.141 Formation of a number of
palladium thiolate species [Pd(ZR)2]n was observed. The
palladium cluster (n = 6) was isolated and characterized by X-
ray analysis. Polymeric palladium frameworks were isolated as
nanoparticles and characterized by electronic microscopy. The
dynamic nature of the catalytic system generated upon the
reaction of Pd(OAc)2 with thiols or selenoles was observed
with cocktail-type behavior (see Section 3 for a mechanistic
discussion). Dynamic exchange of the ZR groups on the
catalyst surface and significant sensitivity of metal−chalcogen
bond strength to the chalcogen atom (Z) and to the nature of
the substituent (R) made it possible to carry out selective
Figure 55. Combination of photocatalysis and TM catalysis.
reactions starting from the mixture of starting material (a
model of a naturally occurring feedstock). Adaptive recog-
nition of S−H/Se−H groups and catalytic regioselective
addition reactions were efficiently performed in a one-pot
(Scheme 273, B).698 Recycling in six cycles proceeds with a manner (Scheme 274). The developed system represents a rare
minimal loss of the product yield. The combination of the two example when heterogeneous catalysts are more selective than
cycles is shown in Figure 55. homogeneous catalysts of a similar nature.141 The influence of
Reiser and co-workers described photocatalysis by Cu and Ir catalyst morphology and degree of ordering of nanoparticles
in the reaction of alkenes with sulfonyl chloride, producing β- for the heterogeneous catalytic system were evaluated.892 A
hydroxysulfones. According to the equation, the reaction heterogeneous Pd/graphene catalyst precursor was tested for
proceeds with bifunctionalization of the double bonds performing addition of benzenethiol to phenylaceylene.893
(Scheme 273, C).890
An interesting approach for C(sp3)−H and C(sp2)−H bond Scheme 275
thiolation in allylic and vinylic derivatives was reported using
CdSe quantum dots and visible light.891 It should be pointed
out that only a few representative examples directly connected
with the section topic were considered here. Rapid develop-
ment of photoredox catalysis is described in a number of
reviews elsewhere. These discussions are not repeated in the
present review.
5. CATALYTIC Z−H BOND ADDITION REACTIONS (Z Simple and easy-to-access catalytic systems based on
= S, Se, Te) palladium acetate were also efficient in the cyclization
Catalytic Z−H bond addition reactions are discussed here, reactions. Synthesis of the 1,3-oxathiine core was performed
focusing on the most representative examples published after in sequential Pd-catalyzed hydrothiolation followed by intra-
the publication of our previous review (literature coverage after molecular cyclization (Scheme 275).894 Regioselective hydro-
2011). The reactions are divided into sections depending on thiolation followed by cyclization was reported for the
the metal catalyst. Most of the publications concern reactions synthesis of substituted tetrahydropyran-4-ones.895 An intra-
involving alkynes, while selective catalytic Z−H bond additions molecular cyclization reaction was efficiently performed in the
to alkenes and other unsaturated molecules are rarely PdI2/KI catalytic system and resulted in the formation of
performed. The addition of S−H bonds (hydrothiolation) substituted thiopenes.896
appears to be the most studied process; the addition of Se−H Utilization of phosphorus-containing ligands is a well-
bonds (hydroselenation) is significantly less studied; while the recognized possibility to tune the reactivity of palladium
addition of Te−H bonds (hydrotelluration) is not sufficiently complexes in Z−H addition reactions. A new oxapalladacycle
described in the modern literature. type of palladium catalyst for Z−H bond addition to terminal
alkynes was reported (Scheme 276).897 An interesting catalytic
Scheme 274 cycle was suggested involving opening/closing of the
oxapalladacycle to act as a hydrogen atom shuttle.
As a simple metal precursor, palladium chloride, was also
involved in the presence of catalytic amounts of strong acids
(Scheme 277).898 The addition of substituted tetrazole-5-thiols
to terminal alkynes was studied. The reaction route and
geometry of the synthesized vinyl sulfides depended on the
type of terminal alkyne used. The alkyne with a strong
electron-withdrawing substituent changed the regioselectivity
of the insertion reaction toward the anti-Martkovnikov isomer.
Chem. Rev. 2022, 122, 16110−16293
Scheme 276
Scheme 277
Scheme 278
Scheme 279
In the presence of PPh3 as a ligand, palladium acetate was 280).901 Typically, Pd-catalyzed hydrothiolation is expected to
used as a catalyst precursor to perform a one-pot stepwise give Markovnikov-type proteins. However, a preferential anti-
coupling−annulation reaction (Scheme 278).899 Sodium Markovnikov reaction was observed with the ligand and
sulfide was involved as a source of sulfur atoms, and a new reaction conditions used. Several alkyne/thiol combinations
C(sp2)−S bond was formed in the product. A number of were studied, and the formation of different products with
benzo[b][1,6]naphthyridines were prepared in a Pd-catalyzed varying selectivity was observed.901
one-pot stepwise process. NHC ligands have also been used to increase the diversity of
The addition of PEt3 as a ligand tuned the reactivity of palladium catalytic systems. A general methodology was
palladium complexes to perform P−S bond addition to reported to carry out selective Markovnikov-type hydro-
terminal alkynes (Scheme 279).900 The overall selectivity was thiolation of alkynes with aliphatic, benzylic, and aromatic
dependent on the reaction conditions, with the sulfur atom thiols.902 Regioselective addition of thiols to cyclopropyl
attached to a more substituted alkyne position. acetylenes was performed using the Pd/NHC complex as a
Interestingly, the PdL2Cl2 complex with the L = 1- precatalyst (Scheme 281).140 Densely functionalized cyclo-
(dicyclohexylphosphanyl)piperidine ligand resulted in a propyl vinyl sulfides were prepared with high selectivity (up to
change in the regioselectivity of the addition reaction (Scheme 99:1) and high yields (up to 99%). A computational study with
Chem. Rev. 2022, 122, 16110−16293
Scheme 280
Scheme 281
Scheme 282
Scheme 283
molecular dynamics simulations of alkyne insertion into the extraction of alkynes from a model petroleum medium in view
Pd−S bond was carried out and identified key factors of the possible practical employment of naturally occurring
controlling the remarkable regioselectivity of the addition sources of thiols.903
process. The (IMes)Pd(acac)Cl complex was found to be a Palladium acetate as a catalyst (2 mol %) and Cu(OTf)2 as
convenient and practical catalyst precursor (IMes = N,N′- an additive (5 mol %) were studied for performing the
bis(2,4,6-trimethylphenyl)imidazole-2-ylidene).140 The same hydrothiolation process in a bimetallic system (Scheme
(IMes)Pd(acac)Cl complex was also utilized for the selective 282).904 A copper salt was proposed to facilitate the
Chem. Rev. 2022, 122, 16110−16293
Scheme 284
Scheme 285
Scheme 286
coordination of a carbon−carbon multiple bond to the Pd-catalyzed thiolation was developed using vinyl cyclic
palladium center, where actual hydrothiolation took place. carbonates as substrates.909 Several highly relevant practical
The system was efficient not only in the hydrothiolation of advantages, such as selectivity, good yields, good product
terminal alkynes leading to vinyl sulfides but also in the scope, and operational simplicity, were achieved.
hydrothiolation of terminal olefins resulting in alkyl sulfides 5.2. Rhodium and Iridium-Catalyzed Transformations
(Scheme 282). Wilkinson’s catalyst chloridotris(triphenylphosphine)rhodium-
The synthesis of alkyl sulfides was performed in various Pd- (I) has been continuously used for carrying out the addition of
containing catalytic systems. Double hydrothiolation of Z−H bonds to unsaturated organic molecules. Love and co-
terminal alkynes was carried out in a regioselective manner workers utilized Rh(PPh3)3Cl as a catalyst precursor for
and afforded the corresponding dithioketal products (Scheme carrying out selective hydrothiolation in the total synthesis of
283).905 It was proposed that Pd-catalyzed double hydro- K777 (a potent cysteine protease inhibitor) and a series of
thiolation proceeded through the formation of vinyl sulfides, analogues (Scheme 286).910 Compared to the Pd-catalyzed
whereas the second thiol addition was promoted by additives reactions discussed in the previous section (branched
(H2O or AcOH). Markovnikov-type vinyl sulfide is a typical product), the Rh-
Samec and co-workers developed a series of atom-efficient catalyzed transformation provides access to (E)-linear vinyl
procedures for the synthesis of keto thioethers through tandem sulfides.
gold/palladium catalysis (Scheme 284).906 A diversity of cyclic Rh-catalyzed highly regio- and stereoselective hydroselena-
and acyclic tertiary sulfenylated ketones were obtained in good tion of internal alkynes with an electron-withdrawing group
to excellent yields. A valuable application for the synthesis of resulted in (E)-vinyl selenides in good yields.911 Catalytic
amounts of RhCl(PPh3)3 and Ph2P(O)H were used to carry
D-ring-expanded steroids was demonstrated.906 Tandem Pd/
out the reaction. The application of different phosphine ligads
Au catalysis was studied in more detail to access a variety of α-
made it possible to tune the Rh-catalyzed reactions to perform
sulfenylated carbonyl compounds.907 A two-step process, the hydrothiolation of alkynes in aqueous media912 and the
including Pd-catalyzed hydrothiolation of propargylic alcohols transformation of terminal alkynes to branched allylic
and enantioselective Rh-catalyzed isomerization of allylic sulfones.913
alcohols, was developed to synthesize chiral α-sulfenylated It should be emphasized that catalyst activity and selectivity
ketones (Scheme 285).908 Good enantioselectivities were are maintained upon heterogenization on a suitable surface.
possible to obtain in some cases (for example, 87:13 and The Rh complex supported on mesoporous SBA-15 silica
>99:1 er). demonstrated good activity even at 25 °C and gave vinyl
Chem. Rev. 2022, 122, 16110−16293
Scheme 287
Scheme 288
Scheme 289
sulfides in good yield and excellent selectivity.914 Rh-P-SBA-15 enhanced α-selective alkyne hydrothiolation919 and the role
was recovered by filtration and reused 6 times in the of carbonyl ligands920 were reported.
hydrothiolation reaction without a loss of catalytic activity Rh-catalyzed Z-selective hydrothiolation of 1,3-disubstituted
and regioselectivity. Possible structures formed upon immobi- allenes was carried out using a catalytic system with a 1,4-
lization of Wilkinson’s catalyst on functionalized SBA-15 silica bis(diphenylphosphino)butane (dppb) ligand.921 Excellent
were studied, and application in hydrothiolation and hydro- selectivity, tolerance to functional groups, and the possibility
sulfonation reactions was reported.915 of dynamic kinetic resolution are important advantages of this
In another example, heterogenization of a rhodium complex catalytic system.
on a support to form [MCM-41-2P-RhCl(PPh3)] was An interesting mechanistic study on the counterion-
performed to carry out hydrothiolation of alkynes.916 The controlled regioselectivity of Rh-catalyzed hydrothiolation of
supported rhodium complex afforded (E)-vinyl sulfides under 1,3-dienes was reported.922 The application of noncoordinat-
ing counterions (i.e., SbF6−) led to the formation of allylic
mild reaction conditions at 40 °C in good to high yields.
sulfides, whereas coordinating counterions (i.e., Cl−) resulted
Castarlenas, Oro, and co-workers have performed a series of
in the formation of homoallylic sulfides. A theoretical study on
studies to elucidate the mechanisms of Rh-catalyzed reactions
the origins of regioselectivity in the Rh-catalyzed hydro-
and develop new synthetic applications.917,918 Interestingly, a
thiolation of 1,3-dienes was described.923
change in regioselectivity from linear to Markovnikov-type Interestingly, the Rh complex with a CNC−pincer ligand
products was observed when a mononuclear catalyst precursor (based on 1,2,3-triazol-5-ylidenes) was efficient in a series of
was used instead of a dinuclear catalyst precursor (Scheme reactions.924 Homodimerization of terminal alkynes took place
287).917 The ligand arrangement in the coordination sphere of in the absence of a thiol, while alkyne hydrothiolation was
rhodium controlled the direction of the addition process and performed in the presence of a thiol (Scheme 288). A
involved alkyne insertion into the Rh−S bond in the rate- sequential alkyne dimerization−hydrothiolation tandem reac-
determining step. Using hydroxodinuclear Rh complexes tion was also successfully carried out.924 Cationic and neutral
[Rh(μ-OH)(NHC)(η2-olefin)]2 (enhanced by pyridine addi- rhodium complexes with N-donor-functionalized 1,2,3-triazol-
tion to dissociate to the mononuclear form), it was possible to 5-ylidene ligands were studied for application in catalysis, and a
direct the reaction toward the formation of Markovnikov-type neutral dicarbonyl complex was shown to be selective for
products.918 A detailed mechanistic study of pyridine- hydrothiolation of an alkyne with an aryl thiol.925,926
Chem. Rev. 2022, 122, 16110−16293
Scheme 290
Scheme 291
Scheme 292
Scheme 293
Rh-mediated transformations were utilized for the design of 290).929 The reaction between the aromatic diynes and
catalytic systems for materials science applications. Ogawa and aliphatic dithiols resulted in polymers with molecular weights
co-workers succeeded in the synthesis of sulfur-containing π- Mw up to 199 000. The obtained polymers were found to be
conjugated polymers.927 Rh-catalyzed hydrothiolation was chemically modifiable with hydrogenation or oxidation
applied for polymerization upon a reaction between 2,5- reactions.
diethynylthiophene and benzene-1,4-dithiol (Scheme 289).927 It was found that Ir complexes can also possess catalytic
The preparation of poly(phenylenevinylene sulfide) was activity in the alkyne hydrothiolation, although the activity was
reported using stereo- and regioselective copolymerization of lower as compared to the Rh analogues (Scheme 291).926 The
dialkynylbenzene and benzenedithiol.928 authors have reported that the studied Rh(I) complexes
Vinyl-sulfide-based polymers were prepared by using the outperformed the similar Ir(I) complexes in terms of activity
thiol−yne click methodology with Rh catalyst (Scheme and selectivity.926
Chem. Rev. 2022, 122, 16110−16293
Scheme 294
Scheme 295
Scheme 296
However, Ir complexes can be synthetically very important A simple Cu(I) catalyst precursor was also employed to
when photoredox conditions are applied. Glorius and co- synthesize α-sulfenylated carbonyl compounds935 as well as for
workers have developed an Ir photoredox catalytic system for the preparation of vinyl sulfones.936
carrying out hydrothiolation of alkenes (Scheme 292).930 The Cu/NHC complex grafted to SBA-15 silica was utilized
Formal addition of the Z−H bond to alkene was accomplished for the catalytic hydrothiolation of alkynes (Scheme 295) and
electron-deficient alkenes under mild conditions.937 The
using the Z−Z reagent (disulfide) as a starting material. The
reaction was performed in good to high yields with preferable
developed disulfide-ene reaction was highly efficient and Z-selectivity. The developed protocol was also expanded to
demonstrated excellent functional group tolerance. Trifluor- include cyclic electron-deficient alkenes as substrates for the
omethylthiolation of styrenes with visible-light-induced photo- thiol addition.
redox/halide catalysis was also reported by the same group.931 The studies of Cu-mediated addition reactions were not
Ir-catalyzed asymmetric addition of aryl thiols was achieved limited to alkynes and alkenes. Cu(OTf)2 was tested for
with an [Ir(cod)2BF4]/(S)-xylbinap catalytic system.932 The catalytic activity in the hydrothiolation of a diene,938 and CuO
products were obtained in high yields (up to 97%) and in nanoparticles were tested for the hydrothiolation of dialkyl
excellent enantioselectivities (up to 98% ee). azodicarboxylates.939 Copper catalysis was also efficient in C−
S bond formation in the addition reaction involving alkynes
5.3. Copper-Catalyzed Transformations
and sulfonyl chlorides.940
The Cu-catalyzed reaction between the thiol and terminal 5.4. Other Metals As Catalysts
alkynes provides an excellent opportunity to access Z-β-vinyl
5.4.1. Nickel. Reisman and co-workers utilized Markovni-
sulfides (Scheme 293).933 In such a case, the reaction proceeds kov-type hydrothiolation of alkynes in a study devoted to
as an anti-addition of the thiol across the triple bond of the enantioselective total synthesis of (+)-Psiguadial B.941 The
alkyne. The same Cu(I) catalyst also facilitates isomerization of nickel-catalyzed reaction proceeded with good regioselectivity
Z-isomers into E-isomers. Thus, E-isomers of alkenylsulfides (Scheme 296).
may also be obtained with good selectivity in some cases. The Taniguchi and co-workers have evaluated the strategy of
reaction was performed for terminal and internal alkynes using dihydrosulfenylation of alkynes, which involves a rapid
a simple Cu(I) salt as a catalyst precursor.
An unusual approach was suggested to control the selectivity Scheme 297
of the Cu-catalyzed hydrothiolation reaction (Scheme 294).934
As reported by the authors, the stereoselectivity of the addition
process was determined by the presence/absence of a CO2
atmosphere. Reversible alkyne carboxylation was proposed as a
possible mechanism to account for the role of carbon dioxide.
Chem. Rev. 2022, 122, 16110−16293
hydrothiolation of the alkyne as a fast step and relatively slow
hydrothiolation of alkenes as a second slow step.942 For some

Scheme 301
Scheme 298
Scheme 302
alkynes both steps can proceed with good regioselectivity and
produce anti-Markovnikov-type dithioacetals (Scheme 297).
Ni-catalyzed hydrothiolation of alkynes was tested as a
model reaction in the development of customized laboratory
equipment by 3D printing.943 Good compatibility with additive
Scheme 299
catalyst precursor.946 anti-Markovnikov-type selective hydro-

thiolation was performed with the product formation in good
to high yields.
technologies was demonstrated, and the reaction retained high Scheme 303
regioselectivity under mild conditions (Scheme 298).
5.4.2. Cobalt. Magnetic metal nanoparticles stabilized by
ionic liquids represent a promising approach to design reusable
catalytic systems.944 Cobalt nanoparticles (prepared from
CoCl2) in a [bmim][BF4] ionic liquid were successfully used
to carry out anti-Markovnikov S−H bond addition to alkynes
and alekenes (Scheme 299).
Ligand control of molecular cobalt complexes made it
possible to initiate various reaction routes.945 Three different
possibilities in the synthesis of carbocyclic organosulfur A simple catalyst precursor such as AuCl was efficiently
compounds were demonstrated from 1,6-enynes and thiols utilized in a number of addition reactions and provided a
(Scheme 300). Using BINAP, Xantphos, and DPPP phosphine synthetic route to α-sulfenylated carbonyl compounds from
ligands and 5 mol % of CoBr2, three different cyclization propargylic alcohols and aryl thiols (Scheme 301).947,948
products were accessed. Selective modification of peptides using allenes as a reagent
5.4.3. Gold. Gold-catalyzed S−H bond addition to was achived with gold catalysis in the presense of a silver salt
unactivated alkenes was possible using PPh3AuNTf2 as a (Scheme 302).949
Scheme 300
Chem. Rev. 2022, 122, 16110−16293
Scheme 305
Scheme 309
5.4.4. Zinc. Zinc iodide as a catalyst precursor in the

presence of 4-toluenesulfonic acid mediated regioselective
hydrothiolation of alkenes with thiols (Scheme 303).950 The
Scheme 306 atoms. Addition of thiols to allenols led to the C−S bond
formation, and the process was accompanied by elimination of
water (Scheme 308).957 Overall, a synthetically useful
dehydrative thiolation of allenols was developed. The
procedure was developed by continuing the study of a gold-
catalyzed thioetherification reaction.958
5.4.7. Manganese. Manganese salts were utilized in the
catalytic cyclization reactions, leading to the formation of
thiolated indenones (Scheme 309).959 The reaction possibly
involves Mn-induced formation of a thiophenoxyl radical and
subsequent addition and cyclization steps.
Intermolecular oxidative cyclization of alkynes and thio-
phenols provided a synthetic pathway to a variety of
functionalized benzothiophenes (Scheme 310).960 The reac-
preparation of dithioacetals from vinyl ethers and the gram- tion took place in the presence of oxygen and was
scale reaction were shown. Zinc-catalyzed double S−H bond accompanied by release of hydrogen peroxide. Synthesis of
addition to the alkynes was developed for the synthesis of C3-sulfenated indoles was carried out by a Mn-mediated
dithioacetals (Scheme 304).951,952 oxidative cascade reaction.961
5.4.5. Iron. Magnetite nanoparticles, as a recyclable catalyst, 5.4.8. Cerium. Anhydrous CeCl3 can be used as a catalyst
were used for regioselective addition of aromatic thiols and for the S−H bond addition to alkynes under solvent-free
aliphatic thiols to alkynes uder solvent-free conditions conditions (Scheme 311).962 In most of the studied cases good
stereoselectivity toward the formation of Z-isomers was
Scheme 307 observed.
5.4.9. Ruthenium. Hydrothiolation of terminal alkynes
with aliphatic or aromatic thiols was carred out in anti-
Markovnikov fashion with a Ru(II) p-cymene catalyst in
aqueous THF (Scheme 312).963 The addition reaction led to
E-linear vinyl sulfides in good to high yields.
5.4.10. Scandium. Using scandium(III) triflate as a
catalyst precursor, hydrothiolation of functionalized olefins
(Scheme 305).953 Intermolecular hydrothiolation of the triple was carried out with anti-Markovnikov regioselectivity.964 High
bond of internal alkynes followed by a cyclization reaction in isolated yields, good functional group tolerance, relatively short
intramolecular fashion resulted in the synthesis of several types reaction time, and mild solvent-free conditions are important
of 1,3-oxathiine derivatives (Scheme 306).954 practical advantages of this procedure. With the developed
5.4.6. Indium. Depending on the nature of the thiol, protocol, hydrothiolation of allyl ethers with a hydroxyl group
indium-catalyzed transformation can produce Markovnikov and perfluorinated ethers and hydrothiolation of allyl esters
and anti-Markovnikov types of products.955 It is of interest that were shown to proceed with good selectivity.
a subtle change in the strucutres of the thiol may cause such a 5.5. Photoredox Processes in Z−H Bond Addition
noticeable change in regioselectivity. Involving Transition Metal Complexes
Selective hydrothiolation of bromoalkynes was performed As mentioned above, photochemical processes and photoredox
with an indium catalyst (Scheme 307).956 The reaction was catalysis with the involvement of sulfur species represent a
tolerant to the presence of C(SP)−Br and C(SP2)−Br halogen great area with many developments. Here, we briefly show a
Chem. Rev. 2022, 122, 16110−16293
Scheme 310
Scheme 311
Scheme 312
Scheme 313
Scheme 314
Scheme 315
few examples related to the process of Z−H bond addition. radicals with improved efficiency.966 This study provides an
The discussions already covered in the literature in other interesting approach for hydrothiolation reactions based on
reviews will not be repeated here. semiconductor photocatalysis.
Ir2S3/ZnIn2S4 nanocomposites were used to carry out Tunable luminescent iridium(III) complexes were studied in
visible-light-initiated hydrothiolation of alkynes and alkenes the hydrothiolation of alkenes with benzyl thiols (Scheme
(Scheme 313).965 The good performance of the Ir2S3/ZnIn2S4 314).967 The studied iridium complexes were found to be
nanocomposite was explained by the photogeneration of thiyl suitable for photocatalysts in photooxidation and photo-
Chem. Rev. 2022, 122, 16110−16293
Scheme 316
Scheme 317
Scheme 318
reduction reactions. Good product yields were found using 0.3 Utilizing Ru(bpy)3Cl2 and blue LED light formation of one
mol % of the catalyst. C−S was reported starting from alkenes, sodium sulfinates, and
The presence of an easily oxidizable arylsulfide functional pyridinium salts.972
group in the vinyl sulfides facilitates the photocatalytic
generation of alkene radical cations that can further undergo 6. CATALYTIC Z−Z AND C−Z BOND ADDITION
cycloaddition reactions with electron-rich reactants.968 REACTIONS (Z = S, Se, Te)
Addition of thiols to alkenes in anti-Markovnikov fashion In the present section, we discuss catalytic reactions involving
was performed using Ru(bpz)3(PF6)2 as a visible-light- Z−Z, C−Z, and Z−X bond activation that lead to the
absorbing photocatalyst (Scheme 315).969 In the studied construction of new C−Z bonds. Indeed, the universality of
process, thiyl radical intermediates were generated upon addition reaction methodology allows the involvement of not
quenching of photoexcited Ru*(bpz)32+ species with thiols. only Z−Z bonds but also C−Z bonds in synthetic procedures.
Markovnikov-type S−H bond addition to alkenes was In the case of Z−Z bond addition, the reaction mechanism
performed by photoredox/cobalt catalysis in a directing- includes Z−Z oxidative addition and multiple bond insertions
group-assisted procedure (Scheme 316).970 The presence of into the M−Z bond, followed by C−Z reductive elimination.
a protective group was important to ensure the required However, in the case of C−Z bond addition, the reaction
coordination of the reactant to the metal center. Another mechanism may include C−Z oxidative addition and multiple
reactant, the thiol, is oxidized by the excited photocatalyst to bond insertions into the M−Z or M−C bond, followed by C−
generate the thiyl radical cation and afford metal-mediated C− C or C−Z reductive elimination. A general mechanistic
S bond formation. The possibility for gram-scale synthesis was framework of the catalytic addition reactions is discussed in
demonstrated. Section 3; here, we focus on the synthetic methodology.
As a related reaction, hydrosulfonylation of alkenes was 6.1. Palladium-Catalyzed Transformations
performed with an Ir photocatalyst and involved sulfonyl Pd-catalyzed bis-selenation of terminal alkynes can be easily
chlorides under visible-light activation.971 The reaction did not performed using Pd(OAc)2 and PPh3 as a metal salt and
involve direct S−H bond addition, but the approach developed ligand, which form the catalytic system in situ (Scheme
is very useful for radical hydrosulfonylation of alkenes. 317).973 A classical methodology developed by Ogawa,
Chem. Rev. 2022, 122, 16110−16293
Scheme 319
Scheme 320
Sonoda, and co-workers974 was utilized for Se−Se bond plexes were formed in good to high yields of 49−82% (Scheme
addition and led to bis-seleno-substituted alkenes in good 318).975
yields and excellent stereoselectivity. Subsequent oxidation of Bisthiolation of alkynes was performed in a three-
(Z)-1,2-bis(arylseleno)-1-alkenes with meta-chloroperbenzoic component system using sodium thiosulfate (Na2S2O3) as
acid (mCPBA) was accompanied by selenoxide elimination the sulfur source and arylhydrazines as a source of the aryl
and resulted in alkynyl selenides (Scheme 317). In the first groups.977 Then, 0.5 mol % of the Pd/NHC complex was
stage, (Z)-1,2-bis(arylseleno)-1-alkenes was synthesized in added as a catalyst precursor, and the reaction was performed
75−83% yields. In the second stage, alkynyl selenides were in ionic liquid media at 120 °C. Three-component
prepared in 56−80% yields.973 Interestingly, intramolecular bisthiolation of terminal alkynes was carried out with a Pd/
Se···O interactions were found to play an important role in the NHC complex as a precatalyst, K2S as a sulfur source, and
formation of products. diaryliodonium salts as a source of aryl groups.978 The
The high functional group tolerance of Z−Z bond addition [C2OHmim]Cl ionic liquid was used as an additive to
concerns not only organic functional groups but also the promote the reaction.
presence of other metals and organometallic structures. An The Pd/NHC complex catalyzed the reaction between
interesting example was demonstrated by palladium-catalyzed azolyl sulfides and terminal alkynes to give (Z)-2-(azolyl)-
bisthiolation of platinum acetylides (Scheme 318).975 Sig- alkenyl sulfides with excellent regio- and stereoselectivities.979
nificant differences in the reactivity of terminal and internal The reaction proceeds with direct cleavage of the C−S bond
triple bonds governed the addition of organic disulfides with followed by alkyne insertion and heteroaryl-vinyl reductive
high chemoselectivity. The mechanistic difference in the elimination.
reactivity of terminal and internal triple bonds of alkynes in Further developed catalytic carbothiolation of terminal
the Z−Z bond addition reactions is an interesting topic studied alkynes was successfully carried out using Pd complexes with
previously.976 The high stereoselectivity of the addition NHC ligands (Scheme 319).980 Competitive alkyne dimeriza-
reaction determined the Z-geometry of forming vinyl groups. tion often proceeds rapidly and imposes a serious obstacle in
Sulfur-containing platinum(II) bis(alkenylarylacetylide) com- carrying out carbothiolation processes. Thus, for selective
Chem. Rev. 2022, 122, 16110−16293
Scheme 321
Scheme 322
carbothiolation, undesired dimerization of alkynes should be performed in a tandem fashion. The overall reactions proceed
suppressed. A favorable combination of reagents with as the incorporation of two boronic acid residues and the
optimized relative reactivity was a key finding. Reactive sulfur reincorporation of the sulfenyl moiety. A useful reaction
derivatives with a Cheteroaryl−SR1 group and difficult-to- related to C−Z bond addition and Pd-catalyzed regio- and
dimerize alkylacetylenes were selected (Scheme 319).975 The stereoselective addition of sulfenyl chlorides to terminal
overall process was performed with high regio- and stereo- alkynes can be mentioned.991
selectivity in good yields. 6.2. Nickel-Catalyzed Transformations
Pd-catalyzed alkynylthiolation of alkynes with triisopropylsi-
lylethynyl sulfide was reported.981 The process was performed The high catalytic activity of Ni centers renders the
as a cis-addition to the triple bond of the alkyne with the development of practical homogeneous and heterogeneous
breakage of the C−S bond and the formation of a C−C bond catalytic systems. Interestingly, the catalytic activity of Ni
and a new C−S bond. Not limited to alkynes, other centers is retained in the metal−organic framework (MOF)
unsaturated molecules may also undergo Pd-catalyzed structure (Scheme 322).992 Specific interactions with gaseous
insertion into the C−S bond.982 molecules is a specific feature of MOF structures, explored on
Pd-catalyzed carboselenation (cyanochalcogenation) of the application of Ni-MOFs for S-functionalization of
alkynes with chalcogenocyanates was reported by Ogawa and acetylene. The Ni-MOF-74 catalyst was efficient in diaryl
co-workers, leading to the simultaneous introduction of thio disulfide addition to gaseous acetylene and resulted in excellent
and cyano groups.983 [Pd(PPh3)4] and [Co2(CO)8] were selectivity. The catalyst was easily separated and recycled with
utilized as catalysts and governed the transformation with high no leaching of Ni species into solution observed.
regioselectivity. A synthetic procedure for Pd-catalyzed
cyanothiolation of internal alkynes was designed based on Scheme 323
tert-butyl isocyanide and organic disulfides.984
Werz and co-workers developed a versatile Pd-catalyzed
carboselenation (cyanochalcogenation) reaction with a catalyst
prepared in situ from Pd2dba3 and a XantPhos ligand (Scheme
320).985 High functional group tolerance expanded the
reaction space to diverse alkynes and aromatic and aliphatic
selonocyanates. The reaction was performed in intra- and
intermolecular fashion, giving Se-substituted acyclic and
heterocyclic derivatives in good to excellent yields (Scheme
320).976 Noncovalent Se···O interactions were revealed in the The reaction with methyl phenyl disulfide led to the
X-ray structure analysis of the products. The same group has formation bisarylthio-substituted product (Scheme 322) and
also reported the efficient Pd-catalyzed cyanosulfenylation of Ph2S2 and Me2S2 as byproducts.980 It appears that the disulfide
alkynes, leading to substituted thienol ethers,986 and developed methathesis process took place under the catalytic conditions.
a powerful synthetic concept.987−989 Under homogeneous conditions, a nickel-catalyzed reaction
An interesting example of Pd-catalyzed breakage of the C−S can be tuned by the nature of the phosphine ligand (Scheme
bond and formation of a new C−S bond upon addition to the 323).993 In the presence of PPh3 as a ligand and Ni(acac)2 as
alkyne unit was reported (Scheme 321).990 The process was an initial source of metal, the reaction with acetylene
accompanied by a Suzuki−Miyaura cross-coupling reaction proceeded as a stereoselective bisthiolation with the formation
Chem. Rev. 2022, 122, 16110−16293
Scheme 324
Scheme 325
Scheme 326
of C−S bonds. Using Ni(acac)2 and PPhCy2 as ligands changes Ni-catalyzed, three-component, regio- and stereoselective
the behavior of the catalytic system and facilitates the carbosulfonylation of terminal alkynes was developed by
formation of C−C and C−S bonds. Bis-sulfur-functionalized Nevado and co-workers (Scheme 325).996 The process utilizes
1,3- diene was obtained in good yields as a triple-component
nickel catalysis for the addition of the SO2R group and
addition reaction (two acetylene molecules and disulfide). In
the mechanistic study, video monitoring with electron attachment of the aromatic groups from boronic acid across
microscopy visualized the transformation of nanoparticles the π system. The overall process involves the formation of C−
and together with a split test and other characterizations S and C−C bonds (and possibly intermediate formation of the
revealed the dynamic nature of the catalytic system.981 C−Cl bond). The reaction is synthetically useful for the
The synthesis of nickel complexes with N,S- or O,S- preparation of a diverse range of products.
coordination modes and possible pathways of their trans-
Nickel-catalyzed carbothiolation of alkynes via the cyclo-
formation, including transformation to nanoparticles, were
studied.994,995 In situ formed Ni(0) complexes and nickel additions of thiophthalic anhydrides was reported.997 Ni-
nanoparticles were evaluated in the catalytic bis-selenation catalyzed reaction of thiocarbamates with internal alkynes to
reaction of terminal and internal alkynes (Scheme 324). access tetrasubstituted vinyl sulfides was developed.998
Chem. Rev. 2022, 122, 16110−16293
Scheme 327
Scheme 328
Scheme 329
Scheme 330
6.3. Rhodium-Catalyzed Transformations sequence, the carbothiolation route in this Rh catalytic system
The Rh-catalyzed carbothiolation reaction of 1-alkylthio-1- can be combined with the initial alkene or alkyne hydro-
alkynes was reported and proceeded via cis-addition with the acylation.
formation of C−S and C−C bonds. 999 Rh-catalyzed In a related methodology, coordination of sulfur atoms to
regioselective alkynylthiolation of alkynes was performed, and the Rh center played an important role in assembling complex
sulfur-directed carbon−sulfur bond cleavage was proposed for structures with sulfur-containing medium-sized rings from
this reaction.1000 An intramolecular version of this reaction linear starting materials.1002
provided the route to the dibenzodithiophene core (seven- 6.4. Copper-Catalyzed Transformations
membered ring with two sulfur atoms).
Yamaguchi and co-workers developed Rh-catalyzed carbo- Lenardao and co-workers reported the stereoselective synthesis
thiolation of 1-alkylthio-1-alkynes (Scheme 326).999 RhH- of (E)-1,2-bischalcogen alkenes based on the addition of
(PPh3)4-dppb was used to design the catalytic system, and the dichalcogenides to terminal alkynes (Scheme 328).1003 CuI/
reaction took place as a cis-addition process. Zn/glycerol was suggested as a recyclable catalytic system
Efficient functionalization of arenes was developed by (reused 5 times), which gave good to high product yields for Z
Weller, Willis, and co-workers using Rh(I) catalysis and = S and Se (trace yields for Z = Te). The possibility of
achieving activating group recycling.1001 Insertion of terminal obtaining bis- and monochalogen-substituted vinyl derivatives
alkynes into aryl ethyl sulfides was performed with high was also studied (Scheme 328). Interestingly, the Pd-catalyzed
selectivity (Scheme 327). In a three-component cascade addition of Z−Z bonds to alkynes results exclusively in Z-
Chem. Rev. 2022, 122, 16110−16293
Scheme 331
Scheme 332
Scheme 333
stereoselectivity, while the Cu-catalyzed reaction gives the using various reagents and conditions.1008−1011 Cu-catalyzed
corresponding E-isomer. synthesis of selenovinyl sulfones was carried out by
Liang and co-workers developed two synthetic protocols selenosulfonation of alkynes.1012 The use of peroxyesters and
based on copper(I) iodide as a catalyst precursor and cesium disulfides as reactants resulted in oxidative intermolecular 1,2-
carbonate as a base (Scheme 329).1004 A regular reaction estersulfenylation of styrenes in a Cu-catalyzed transforma-
under heating in NMP gave tris-seleno-substituted alkenes, tion.1013
whereas under irradiation with white light LEDs in toluene, 6.5. Gold-Catalyzed Transformations
only bis-seleno-substituted alkenes were obtained.
Zeni and co-workers developed a copper-catalyzed cycliza- Efficient Au-catalyzed stereoselective thioallylation of alkynes
tion of propargylpyridines with diorganyl dichalcogenides as a was developed by Shi and co-workers based on redox catalysis
route to 2-(organochalcogenyl)-indolizines (Scheme 330).1005 without the need for a strong oxidant.1014 High yields up to
The protocol showed good functional group tolerance and 99% were achieved using only 0.1 mol % of a catalyst.
proceeded in good yields for diselenides (Z = Se) and Interestingly, as proposed by the authors, the gold(I) species
ditellurides (Z = Te). However, disulfides (Z = S) were act as a π-acid for alkyne activation and as a redox catalyst for
inefficient in this transformation. Further functionalization was Au(I)/(III) coupling. An electrochemical procedure for
performed by involving the RTe group in the Pd-catalyzed promoting Au-catalyzed oxidative coupling of alkynes was
Suzuki−Miyaura cross-coupling reaction. also developed.1015
The CuI/Na2CO3/DMF catalytic system was also utilized in Further development of this methodology resulted in Au-
the synthesis of functionalized indolizinones from substituted catalyzed alkyne and allene diselenation reactions (Scheme
pyridines bearing a ynone framework (Scheme 331).1006 A 332).1016 High trans-regioselectivity of the process and good to
two-component Cu-catalyzed cyclization cascade was efficient excellent yields (up to 98% with 2% catalyst loading) were
in the case of diselenides and disulfides (Z = S and Se). As in demonstrated for a wide range of various substrates.992 Such a
the previous case (Scheme 330), dinuclear copper complexes gold-catalyzed transformation provides access to E-bis-
were proposed as intermediates of the catalytic cycle. selenated products and complements the palladium-catalyzed
Postfunctionalization of the synthesized indolizinones was reaction, which leads to Z-bis-selenated products.
performed by reduction with NaBH4 (Scheme 331). Gold- and photoredox-cocatalyzed thiosulfonylation of
A practical Cu-catalyzed route for the synthesis of β-halo alkynes was developed, leading to the synthesis of diverse
vinylsulfones was reported via a four-component reaction thiofunctionalized vinyl sulfones in good yields and high regio-
involving terminal alkynes, aryldiazonium tetrafluoroborates, a and stereoselectivity (Scheme 333).1017 Tri- and difluoro-
sulfur dioxide surrogate DABCO·(SO2)2, and potassium methyl-thiosulfonylation of alkynes and trifluoromethylthio-
halide.1007 The synthesis of alkenyl sulfones using Cu-catalyzed sulfonylation enynes were implemented using a combination of
reactions is a well-developed area and is usually performed 0.5 mol % of Ph3PAuNTf2 and 0.1 mol % of Ru(bpy)3Cl2 to
Chem. Rev. 2022, 122, 16110−16293
Scheme 334
Scheme 335
Scheme 336
Figure 56. Comparison of the number of studies considered in the previous review published in 2011 (ref 1) and in the present review. (A)
Percentages for these methodologies in the 2011 review, (B) growth rate in the number of studies covered, and (C) percentages for these
methodologies in the present review.
build a catalytic system. The reaction was performed under rt sulfones was carried out with Fe-mediated stereoselective
conditions with blue LED irradiation under an inert halosulfonylation of terminal alkynes upon reaction with
atmosphere. A mechanistic study suggested the possible sulfonylhydrazides.1027 The preparation of vinyl sulfones in
involvement of a gold-mediated sulfonyl radical addition the reaction between sulfonyl hydrazides and alkyne derivatives
pathway. was reported using an Fe/Cu cocatalyzed reaction.1028 An Fe-
Using a similar Au photoredox catalytic system, stereo- catalyzed reaction in the presence of iodine was reported for
selective synthesis of vinyl-chalcogen derivatives was per- the synthesis of chalcogen-containing heterocycles.1029
formed (Scheme 334).1018 Expansion of the reaction to 6.7. Rhenium-Catalyzed Transformations
include selenylation was an important development.
Using an unusual metal as a catalyst, rhenium-catalyzed
PhSO2SePh and PhSO2SPh were reacted with the alkynes
insertion of terminal alkynes into the C−S bond was reported,
under similar conditions. leading to regio- and stereoselective synthesis of γ-thio-α,β-
6.6. Iron-Catalyzed Transformations unsaturated ketones.1030 [HRe(CO)4]n was used as a catalyst
A stereoselective route for diselenide addition to terminal and precursor, and the reaction proceeded in an intramolecular
internal phenylacetylene derivatives was developed using FeCl3 fashion.
as a catalyst precursor and nitromethane as a solvent (Scheme
335).1019 Bisvinyl selenides were obtained with E-geometry 7. COMPARISON OF RESEARCH TRENDS OVER THE
arrangement, and the reaction took place at rt. RECENT DECADE
Fe-catalyzed addition of the Z−Z bond was accompanied by The previous review on this topic was published a decade ago
cyclization of alkynols, leading to five- or six-membered in 2011 (ref 1), and it is, of course, of much interest to
heterocyclic cores (Scheme 336).1020 The system was compare the main trends in comparison with the present
compatible with diselenides and disulfides (Z = S, Se) but review. In the literature summarized up to 2011, approximately
was not efficient for ditellurides (Z = Te). 70% of studies were devoted to cross-coupling, and
Z−Z bond addition reactions to alkynes were also approximately 30% of studies were devoted to addition
performed with large metal loadings.1021−1025 Fe-catalyzed reactions in C−Z bond formation (Figure 56, A). During the
chlorosulfonylation of terminal alkynes was performed in a time period between 2011 and 2021, the number of studies in
regio- and stereoselective manner using aromatic sulfonyl the cross-coupling reaction underwent very high ∼200%
chlorides.1026 Synthesis of (E)-β-chloro and bromo vinyl- growth (Figure 56, B). The number of studies in the addition
Chem. Rev. 2022, 122, 16110−16293
Figure 57. Comparison of catalysts according to the number of studies considered in the previous review published in 2011 (ref 1) and in the
present review. (A) Percentages for metal catalysts in the 2011 review, (B) growth rate in the number of studies covered, and (C) percentages for
metal catalysts in the present review.
reactions was grown by approximately 40%. Thus, in the selectivity and desired efficiency. The search for cost-efficiency
present review, the ratio between these two methodologies was provided a driving force to explore different metals, with a
changed to approximately 85% for cross-coupling and 15% for particular focus on cheap and easily available metals. Indeed,
addition reactions. It appears that cross-coupling reactions the synthetic potential of the considered reactions can now be
provide the major driving force for the development of this fully realized in the application prospects.
field. In contrast, addition reactions occupy a certain niche, and After our previous review of the field,1 an impressive
the number of studies grows moderately. tremendous development took place, which we summarize and
In the literature covered in 2011 for the most used cross- provide outlines in the three following sections: achievements,
coupling methodology, Pd-catalyzed reactions were a signifi- problems, and challenges.
cant part of the studies (∼35%); the most used metal was Achievements
copper (50%); a smaller number of nickel catalysts were
involved (∼7%); and the share for the other metals altogether (i) For some time, catalytic C−S bond formation was in the
was approximately 8% (Figure 57, A). Over the recent decade, shadow of other C−heteroatom bond formations since
palladium catalysts have still been actively used and underwent dedicated catalytic systems were not developed and
some development with a growth rate of approximately 90%, sulfur was considered a poison for catalysis. However,
while a much higher growth rate was observed for copper- the past period has changed this feeling, and catalytic
(∼230%) and nickel- (∼280%) based catalysts (Figure 57, B). C−S bond formation is now a standalone field as well as
The most exciting growth rate (∼500%) was observed for the an indispensable toolbox for organic synthesis. The great
involvement of other metals in the catalytic reactions. Thus, practical demand for organosulfur compounds provides
two leading trends�to reduce the cost of the metal catalyst the strongest stimuli for the development of new
and to diversify the metals used for catalysis�can be noted. As synthetic procedures. An even stronger demand for
a result of these trends, the ratio of metal catalysts was sulfur compounds in the areas of drug design, natural
accordingly changed (Figure 57, C). Copper was the most products, biochemistry, and materials science, among
often applied in the catalytic reaction, with palladium as the many other areas, will further push new catalytic systems
second choice, and nearby competitors are represented by to be discovered. Although to a lesser extent, the same is
nickel and other metals. Of course, the discussion in this applicable for organo−selenium and organo−tellurium
section should be considered only from the point of view of compounds, for which new practical applications have
main trends as it reflects the approximation based on the also been revealed.
literature covered. (ii) Palladium-catalyzed transformations still hold the
position of being predictable, robust, and easy to
8. CONCLUSIONS perform with high functional group tolerance, good
Fascinating progress in catalytic C−Z bond formation yields, and excellent selectivity. Ready-to-use synthetic
reactions using two complementary approaches�cross-cou- methodologies for palladium catalysts have been
pling and addition reactions�has been reviewed here for developed for a diversity of classical cross-coupling,
sulfur, selenium, and tellurium. The application prospects of C−H functionalization, Z−Z and Z−H addition
the considered synthetic methodology deserve special note. At reactions, carbothiolations, etc. Precise optimizations of
the beginning period (i.e., in the 90th of the previous century), reaction conditions and a number of well-developed
metal-catalyzed carbon−chalcogene bond formation was ligand types tune the efficiency and utility of Pd-
viewed as a great challenge because sulfur species were catalyzed reactions to the uppermost level. Synthetic
considered strong poisons for metal catalysts. This stage was chemists often consider the Pd-catalyzed route as a
overcome, and helpful catalytic systems were developed for C− method of choice if the procedure is developed and
S bond formation. The methodology was extended to selenium overall cost-efficiency is affordable. To date, palladium is
and tellurium as well. In the next period of development, a the only metal for which extraordinary catalytic activity
variety of metal catalysts were explored, and high selectivity, with a tiny amount of catalyst (i.e., at the ppm level) is
robustness, and functional group tolerance were achieved. known for a large variety of reactions (C−C couplings,
Currently, these catalytic reactions have become a highly Heck reactions, C−Z bond formation, etc.). A reaction
optimizable and rigorously tuned research instrument that can driven by traces of Pd is no longer an unusual event,
be used to focus on particular reactions to obtain excellent while for other metals, there are only a few examples of
Chem. Rev. 2022, 122, 16110−16293
trace activity for synthetic-scale reactions. There is no reaction to another in a regular laboratory environ-
doubt that the applications of Pd catalysis will continue ment.1032 For Pd-free coupling, corresponding control
to develop for the C−Z bond formation reactions experiments should be routinely performed to rule out
considered here. this unwanted option. ICP-EOS/ICP-MS analysis of
(iii) Certainly, currently, Pd is not the only active player in reaction mixtures on Pd and revealing the influence of
the field. The trend in the development of Cu catalysts the addition of small ppm amounts of Pd (i.e., to see if
(also Ni and other metals) noticed for this chemistry a ppm amounts of Pd can in principle influence the
decade ago1 was fully realized in a mature field. The studied reaction) are among the simple control experi-
number of publications on Cu catalysis considered in the ments. Further more detailed studies are possible as well.
present review is significantly larger than that on Pd or (iv) The development of less toxic catalysts and environ-
any other metal. Indeed, Cu-catalyzed reactions have mental concerns are the focus. The hope that “less toxic”
undergone colossal development and growth. The easy light metals (as a replacement for “heavy metals”) can
accessibility and low cost of copper in conjunction with solve the problem has not come true at the moment.
new catalytic opportunities make Cu catalysts a very The toxicity of metal complexes depends on many
attractive aim. Of course, the driving force on the factors and is a complicated topic (see Section 2).
development of cheap catalysts (Cu, Ni, Co, Fe, etc.) Analysis of the bioprofiles of catalytic reactions may be
will continue to be actively developed. one of the options to explore.1033,1034
(iv) A number of interesting particular trends should be Challenges
mentioned. Novel advancements arising from photo-
redox transformations are worth exploring. This is (i) Catalytically active centers are in many cases denoted in
especially true in the case of sulfur, which possesses square brackets as [Pd], [Cu], [Ni], or simply [M].
reach possibilities for radical chemistry. Often, the brackets are omitted; however, the catalyti-
C−C and C−Z bond activation/formation by Ni catalysts cally active centers are shown as MLn, and the meaning
brings new reactivity patterns, empowered by the accessibility remains. In the majority of catalytic reactions, the exact
of various metal oxidation states within a catalytic cycle. structure of the catalytically active center remains
Bimetallic catalysis has demonstrated unique possibilities to unknown. For homogeneous catalysis, ligand dynamics
carry out practically relevant transformations in a one-pot (coordination/dissociation), the formation of metal
manner. dimers and clusters, ligand-bound vs ligand-free catalytic
routes, etc. significantly complicate the mechanistic
Problems
studies. Nanoscale (heterogeneous) catalysis is even
(i) Synthetic procedures with optimized green chemistry more complicated because it includes catalytic centers
metrics are extremely rare. Typical synthetic procedures on the surface as well as the above issues related to
give significant amounts of waste, i.e., 1 g of waste per 1 homogeneous catalysis (because of leaching). Leaching
g of product is a common lower limit estimate only for is very common in the considered catalytic reactions and
the synthetic stage (often it is much more). The use of initiates a homogeneous pathway starting from the
chromatography or similar techniques for product heterogeneous catalyst precursor. A mechanistic under-
separation/purification may further dramatically increase standing of catalytic processes is a big challenge. This
the amount of waste. This is also notable for addition does not mean the absence of progress over the past
reactions, which are advertised as atom-economic by decade. In contrast, a number of excellent mechanistic
design. However, in practical implementations, the studies have been published, and significant insight has
amount of waste produced in addition reactions may been made. A new degree of complexity appeared after
not significantly differ compared to cross-coupling. For revealing the “cocktail”-type nature of many catalytic
both methodologies, an excess of one of the reactants, systems and the possibility of several catalytic routes
solvents, etc. dramatically reduces the green metrics. operating in parallel.
Practical implementations and plausible industrial usage (ii) Principles for rational catalyst design for particular
for fine chemicals will be hindered unless the issue can reactions or synthesis of targeted classes of compounds
be improved. should be developed. Many new catalytic systems have
(ii) Little progress in catalyst recycling was made during the been discovered using empirical approaches, such as
decade. If the amount of catalyst is increased and if the screening ligands, optimizing reaction conditions, or by
reaction is carried out at higher temperature for a longer serendipity. Impressive progress in catalysis has been
time, it is usually possible to show good product yields achieved in recent years using computational modeling,
for approximately 5 cycles. However, it is not real analysis of big data, and application of artificial
catalyst recycling. Measuring kinetic profiles (rate intelligence algorithms. The time is ripe now to connect
constants) rather than product yields would be much this progress with the real needs of synthetic chemists.
more illustrative for assessing catalyst activity in reuse. In (iii) Conceptually, a new generation of active, selective, and
addition, other known procedures are used to assess stable catalysts needs to be developed. This challenge is
catalyst activity and degradation.1031 A long-standing strongly connected with the previous two and calls for
catalyst that can be recycled without a loss of activity groundbreaking breakthrough discoveries.
remains a future target for many transformations. (iv) The development of catalysts for the synthesis of small
(iii) Extraordinarily high activity of palladium at trace levels molecules is, of course, a classical area. Equally
can sometimes be a problem for characterizing the true important currently is to develop catalysts that can
activity of other metal catalysts, especially taking into tolerate not only simple functional groups but also the
account how easy Pd traces may be transferred from one next level of molecular complexity. Catalysts with high
Chem. Rev. 2022, 122, 16110−16293
chemical selectivity for performing the desired reaction Award, Butlerov Golden Medal, and Demidov prize for research.
in large molecular frameworks are now needed. Catalysts Abroad, she also won the Kapitza Award Fellowship (UK) and
operating with atomic precision for large molecular Women in the Engineering Science award (Sweden). She was named
systems could revolutionize the life sciences in a similar Doctor Honoris Causa by the Universities of Córdoba (Argentina)
manner as simple Pd complexes revolutionized the field and Technical of St. Petersburg (Russia), Honorary Professor of the
of organic chemistry. Moscow State University, Honorary Member of the Academy of
The summary provided in the present review highlights Science (Bashkortostane), Professor Honoris Causa of the University
enormous activity in the field over recent years (approximately of Alicante (Spain), Honorary Doctor the Royal Institute of
400 articles were cited in the previous review1 covering the Technology of Stockholm (Sweden), external member of the Royal
whole time period until 2011, and >1000 articles were cited in Academy of Exact, Physical and Natural Sciences (Spain), and
the present review for a time period of approximately 10 Member of the Academia of Europe. For many years, she participated
years). Recently, many studies have been performed aimed at in the activities of the IUPAC and in 1991−1993 was a president of
particular optimization of specific reactions (fine-tuning of the Division of Organic Chemistry and after was a Vice-Chair of the
reaction conditions, minor improvements in the ligands and IUPAC Committee on chemical weapons destruction technology
catalytic systems, just more reactions and substituents, etc.). (CWDT). Now her interest concentrates on the problems of catalysis
From the catalysis advancement perspective, this may give an in organic chemistry.
impression of extensive (incremental) development or even Valentine Ananikov received his Ph.D. in 1999 and Habilitation in
stagnation. However, from another point of view, this is not 2003, and in 2005 he became Laboratory Head of Zelinsky Institute
the case. Rather, it is an impressive realization of synthetic of Organic Chemistry, Russian Academy of Sciences. In 2008 he was
potential in the field of organic synthesis. The catalytic elected as a Member of Russian Academy of Sciences, in 2018 as a
methodology was implemented to solve practical needs. To Member of European Academy (Academia Europaea), and in 2019
illustrate this potential, we have considered many of these elected as Academician of Russian Academy of Sciences. He was a
synthetic transformations in detail in the present review. recipient of the Russian State Prize for Outstanding Achievements in
This was an important and predetermined stage of Science and Technology (2004), an Award of the Science Support
development in catalytic C−Z bond formation, following the Foundation (2005), a Medal of the Russian Academy of Sciences
discovery phase of new catalysts and reactions. However, this (2000), Liebig Lectureship from the German Chemical Society
field should not hang at this stage for too long to avoid real (2010), and Balandin Prize for Outstanding Achievements in
stagnation. Therefore, we have summarized global problems Catalysis (2010). He has been named Actively Cited Researcher�
and challenges to solve. We believe that the field will continue Russia by Thomson Reuters (2015). He was a recipient of the
active development in the near future to gain more Organometallics Distinguished Author Award Lectureship by the
understanding of the mechanisms of catalytic reactions and American Chemical Society (2016), Hitachi High-Technologies
rational design of new generations of catalysts. The great
Award in Appreciation for Novel Approaches and Outstanding
demand for organo−chalcogen compounds leaves no doubt
Contributions to Setting New Standards for Electron Microscopy
about achieving new results in the upcoming decade.
Applications in Chemistry (2016), Reaxys Award Russia (2019), and
Zelinsky Prize for outstanding achievements in organic chemistry
AUTHOR INFORMATION
(2020). His educational activities include the research laboratory at
Corresponding Authors St. Petersburg State University and a professorship at the Chemistry
Irina P. Beletskaya − Chemistry Department, Lomonosov Department of Moscow State University. He has a membership in
Moscow State University, Moscow 119899, Russia; Advisory and Editorial boards of several journals: JACS Au,
Email: beletska@org.chem.msu.ru Angewandte Chemie, International Edition, Chemistry�A European
Valentine P. Ananikov − Zelinsky Institute of Organic Journal, Organometallics, Advanced Synthesis & Catalysis, Chemistry
Chemistry, Russian Academy of Sciences, Moscow 119991, An Asian Journal, OpenChemistry, ChemCatChem, and Russian
Russia; orcid.org/0000-0002-6447-557X; Email: val@ Chemical Reviews. His scientific interests are focused on catalysis,
ioc.ac.ru organic synthesis, molecular complexity, and transformations.
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.chemrev.1c00836 ACKNOWLEDGMENTS
The authors greatly thank Dr. Arina Muraskina, Dr. Kseniya
Notes
Egorova, Liliya Sahharova, Dr. Darya Prima and Alexandra
The authors declare no competing financial interest. Erofeeva for their help with the manuscript preparation.
Biographies
Irina Beletskaya was born in Leningrad (St. Petersburg). She
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Chem. Rev. 2022, 122, 16110−16293

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Transition-Metal-Catalyzed C−S, C−Se, and C−Te Bond Formations

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CONTENTS 4.2.2. Chan−Lam Coupling Reaction with the

© 2022 American Chemical Society https://doi.org/10.1021/acs.chemrev.1c00836

Table 1. Examples of Useful Compounds Containing C−S or C−Se Bonds

be achieved only in the case of selective transformation with

Figure 9. Formation of monometallic species M(ZR)2, metal clusters,

The reaction with α-naphthylthiol and ortho-anisylthiol did

Scheme 6 The recyclable palladium−prolinate complex Pd(L-Pro)2 was

Scheme 21 In a reaction of aryl halides with potassium thiocyanate, an

The same group carried out a similar reaction with

Figure 13. Decarbonylative C(sp2)−S bond formation catalyzed by

recyclization, the yield decreases from 95% to 81% in four

(Scheme 41, E). The nitro group can be reduced by silane to

Figure 14. Oxidative formation of N-aminosulfonamides via a Chan−

mechanism reflects the general processes for the oxidative

Figure 15. Catalyzed by Pd(II) oxidative coupling with arylhy-

which proved to be the best sulfenylating agent under the

In the presence of ortho-Br in the sulfenylating reagent,

Figure 17. Pd/Cu catalysis in C(sp2)−H sulfenylation by ArB(OH)2/

Figure 18. Pd(II)-catalyzed reaction of indole with cyclohexanones

In the presence of salts (NiCl2, LiCl), other products are

Figure 20. Compounds obtained in Ni-catalyzed reactions.

Figure 19. Compounds obtained via Pd(II)-catalyzed C−H activation

A Pd-catalyzed synthesis of dibenzothiophenes from

directing group and a similar electrophilic reagent was carried Scheme 56

A).294 The authors provided evidence of the conversion of

Figure 21. Ruthenium complex B after metalation.

Nishihara and co-workers carried out a reaction of arenes

In the reaction of N-arylsulfonamide with diaryldisulfides

facilitates the cross-coupling step by lowering the activation

Scheme 62. continued

A convenient protocol for thioetherification of aryl and

The possibility of a mechanism in which the catalytic cycle Scheme 65

The production of vinyl sulfides via the Ullmann-type

substituted iodides, which produced high yields (78−99%)

example of divergent regioselectivity controlled by the catalytic

2,2′:6′,2″-terpyridine (Mtpy) at 110 °C (Scheme 70, H).355 Scheme 73

Scheme 79 Using this sulfur source, Sekar and co-workers synthesized

thiolation and Michael addition to a multiple bond followed by

Scheme 91 To prepare thioesters, the authors440 used stable and easily

Scheme 100 A large series of biologically active compounds were

Scheme 111 Scheme 113

Zhao and Cai and co-workers synthesized the C(sp2)−S

Scheme 120 Scheme 122

thiosemicarbazide) leads to symmetric sulfides in a reaction

In a model reaction, recyclization was carried out: three

Scheme 125 Scheme 128

iodides with neutral and electron-withdrawing substituents;

HetSH and AlkSH reacted with PhI with good yields.

Recyclization of the catalyst (5 cycles) proceeded with a

However, both the Ni complex 571 and the copper

Scheme 165. continued

4.2.3.2. Reactions Using Other Sulfur/Selenium Sources.

Disulfenylation of imidazo[1,2-a]pyridines with elemental A three-component reaction of the synthesis of flavone

Figure 37. Thiolation products of maleimides and 3-indolylmaleimides.

The preparation of sulfones in a copper-catalyzed reaction of

Scheme 185 Scheme 188

Figure 39. C−H functionalization in the sulfonylation reaction with

Scheme 187 In a “green environment” (in water or polyethylene glycol),