REVIEWS DOI: 10.1002/adsc.

202100136

Aryldiazonium Salts in Photoredox Catalysis – Recent Trends

Sakamuri Sarath Babu,a P. Muthuraja,a Pooja Yadav,a and
Purushothaman Gopinatha,*
a
Department of Chemistry
Indian Institute of Science Education and Research Tirupati,
Tirupati, A.P. India
E-mail: gopi@iisertirupati.ac.in

Manuscript received: January 30, 2021; Revised manuscript received: February 13, 2021;
Version of record online: Februar 22, 2021

Dedicated to Prof. Srinivasan Chandrasekaran on the occasion of his 75th birthday

Abstract: Aryl diazonium salts are an important 4.3. Oxy-Arylation of Alkynes for the Synthesis of
class of organic compounds that are now widely used Benzofuran
as arylating agents in photoredox catalysis owing to 4.4. Synthesis of Indoles via Amino-Arylation of Alkynes
their lower redox potential, broad substrate scope, 4.5. Synthesis of Biaryls and 2-Arylbenzofuran
and atom economy. They have successfully been used 5. Cross-Coupling Reactions
in many interesting organic transformations to in- 5.1. Alkynylation of Arene Diazonium Salts with Alkynyl
troduce an aryl group. They serve as good alter- Carboxylic Acids
5.2. Cross-Coupling of Aryldiazonium and Sulfinate Salts
natives for aryl halides and other aryl organometallic
5.3. Synthesis of Biaryls
reagents primarily used as aryl group surrogates. New 5.4. Cross-Coupling of Aryl Silanes
reactions using aryl diazonium salts are continually 6. C N Bond Formation
emerging, and in this review, we have highlighted 6.1. Synthesis of Aryl-Azoimidazo-Heteroarenes
some recent developments in photoredox arylations 6.2. Azo-Trifluoromethylation of Alkenes with Aryldiazo-
and their applications. nium Salts and Sodium Triflinate
6.3. Photoredox-Catalyzed Synthesis of Alkylaryldiazenes
1. Introduction 6.4. Synthesis of N-Arylamides
2. Addition Reactions 7. C S Bond Formation
2.1. Addition to Alkenes 7.1. Synthesis of β-Sulfonated Ketone
2.2. Addition to Alkynes 7.2. Synthesis of Sulfonated Thiols from Aryl Diazonium
3. Direct C H Arylation Salts
3.1. Arylation of Anilides using Aryldiazonium Salts 7.3. Synthesis of Arenesulfonyl Chlorides
3.2. Arylation of Simple Phenylureas 7.4. Synthesis of Sulfonated Isobenzofuran-1(3H)-Ones
3.3. C H arylation of (Hetero)Arenes through Aryldiazonium Salts
3.4. C H Arylation of Heteroarenes and Coumarins 7.5. Synthesis of Aryl Sulfides from Aryldiazonium Salts
3.5. C H Arylation of (Hetero)Arenes under Sunlight 7.6. Chemoselective Synthesis of Diaryldisulfides from
3.6. C H Arylation with Anilines via in situ Generated Coupling of Arenediazonium Salts
Diazonium Salts 7.7. Synthesis of S-Aryl Thiosulfonates
3.7. Heterogeneous Photoredox Arylation with Aniline 8. Miscellaneous Reaction
3.8. Metal-Free direct C H Arylation of Aniline 8.1. Mechano-Chemicalborylation of Aryldiazonium Salts
3.9. Metal-Free Intramolecular C H Arylation 8.2. Hydroxycarbonylation from Diazonium Salts
3.10. Metal-Free Direct C H Arylation of 2H-Indazoles 8.3. Copper Promoted Trifluoromethoxylation of Aryldia-
3.11. Metal-Free Direct C H Arylation of Quinoxalin- zonium Salts
2(1H)-One 8.4. Difluoromethylthiolation of Aryldiazonium Salts
3.12. Visible-Light Induced Self-Promoted Arylation of 8.5. Organogold (III) Complexes from Aryldiazonium
BODIPYs Salts
3.13. Direct C H Arylation of Pyridines 8.6. Synthesis of Trifluoromethylselenolated Arenes
3.14. C H arylation of Xanthines with Aryl Azosulfones 9. Conclusion
4. Dual Gold-Photoredox Catalysis
4.1. α-Aryl Enones from Propargyl Alcohols Keywords: Photocatalysis; C H functionalization;
4.2. α-Aryl Enones from TMS-Terminated Alkynols Arylation; Aryl Diazonium salts; Photoredox catalysis

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S. Sarath Babu received his
M.Sc degree in organic
chemistry from S.V University,
Tirupati, India in 2015. He was
a lecturer at Chemistry Depart-
ment, S.V Arts College, Tirupa-
ti, India during 2015–2017. He
is currently pursuing Ph.D at
Indian Institute of Science Edu-
cation and Research, Tirupati,
India under the guidance of
Dr.P. Gopinath. His research
focus is on visible light mediated organic trans-
ormations and dual photo redox catalysis.
Dr. P. Muthuraja completed his
M.Sc (Chemistry) from Madur-
ai Kamaraj University, India.
He was a Research Associate
at Syngene International Pvt
Ltd, Bangalore, from 2009–
2012. He completed his Ph.D
from Alagappa University, Kar-
aikudi, India in 2018 and re-
ceived best thesis award. Cur-
rently he is a Post-doctoral
fellow at Indian Institute of
Science Education and Research, Tirupati, India. His
research interests are organic synthesis, remote C H
activation, polymer chemistry, and photocatalysis.
1. Introduction
Since its discovery in 1858 by Griefs,[1] aryldiazonium
salts have become an indispensable reagent in organic
synthesis with a wide variety of applications.[2] The
importance of aryldiazonium salts in organic synthesis
is evident from several reactions that are associated
with it. In 1884, Sandmeyer used aryl diazonium salts
for the formation of chloro benzenes and bromo
benzenes using CuCl and CuBr, respectively.[3] Later,
in 1896, Pschorr reported the synthesis of phenan-
threnes through an intramolecular cyclization of the in-
situ generated aryl radicals.[4] Following this, Meer-
wein and co-workers in 1939 reported arylation of α,β-
unsaturated carbonyls, and olefins using aryldiazonium
salts and a copper catalyst.[5] Apart from these,
aryldiazonium salts are used in several palladium-
catalyzed cross-coupling reactions for carbon-carbon
and carbon-heteroatom bond formation, replacing aryl
halides.[6]
Since aryl groups are widely present in many
drugs[7] and natural products,[8] several reports using
Adv. Synth. Catal. 2021, 363, 1782 – 1809
Pooja Yadav received her MSc
degree in organic chemistry
from Delhi University, Delhi,
India, in 2018. She is currently
pursuing Ph.D at Institute of
Science Education and Re-
search, Tirupati, India, under
the guidance of Dr. P. Gopi-
nath. Her research focus is on
visible light mediated remote
C H activation using photo-
redox catalysis, and develop-
ment of new synthetic methods.
Dr. P. Gopinath obtained his
Masters degreee (2005) at Uni-
versity of Madras majoring in
Organic chemistry. In 2011, he
obtained his Ph.D at Indian
Institute of Science, Bangalore
in the department of Organic
chemistry. After completing his
Ph.D he worked as a JSPS
postdoctoral researcher at the
Institute of Microbial
Chemistry from 2011–2013. In
2013, he moved to Columbia University to work as
postdoctoral research scientist in the department of
Chemistry. Since 2017, he is working as an assistant
professor at the Indian Institute of Science Education
and research Tirupati. His research interests are
photoredox catalysis, C H functionalizations and new
method developments.
transition metal catalysts on cross-coupling and C H
arylation reactions are reported.[9] However, given the
drawbacks of these traditional methods, such as
additives, oxidants, ligands, elevated temperatures,
etc.,[10] there has always been a growing desire for mild
and alternative approaches.[11] Photoredox catalysis, a
rapidly growing field of catalysis, has revolutionized
organic synthesis for the past decade[12] by using
transition metal-based complexes[13] and organic dyes
as photocatalysts.[14] These photocatalysts use light as
an inexpensive, abundant, non-polluting, and renew-
able source of clean energy. The general mechanism of
action of photoredox catalysis is discussed in several
reviews & articles[15] and is beyond the scope of this
current review.
Photo-catalyzed arylation reactions using aryldiazo-
nium salts were first reported in 1984 by Deronzier. He
reinvestigated Pschorr’s reaction for the synthesis of
phenanthrenes using Ru(bpy)3Cl2 as photocatalyst and
250 W xenon lamp (λ > 410 nm) as a light source
(Scheme 1).[16] Although there are several aryl radical
precursors, such as aryl sulfonyl chloride, diaryl
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Scheme 2. Photocatalytic benzothiophene synthesis.

2.1. Addition to Alkenes

Scheme 1. Evolution of aryldiazonium salt.
iodonium salts, triaryl sulfonium salts, & aryl halides;
aryldiazonium salts are most widely preferred aryl
partners in photoredox catalysis because of their lower
redox potential, reactivity, substrate scope, and atom
economy. New methods of photoredox arylations using
aryldiazonium salts are continually emerging, and to
keep abreast of these developments, a concise report is
highly desirable. This review mainly focuses on the
recent developments in photoredox arylations and their
applications using aryl diazonium salts.
2.1.1. Synthesis of Indole Derivatives from Aryldiazo-
nium Salts
In 2017, Tóth et al. achieved the synthesis of function-
alized indoles from aryldiazonium salts and N-alkyl-N-
aryl-2(trifluromethyl)acrylamides using erythrosine B
(organic dye) as the photocatalyst. The reaction was
performed at 50 °C with blue LEDs using MeOH as
the solvent (Scheme 3).[22] Electron donating groups on
the aryldiazonium salt gave moderate to good yield
while electron-withdrawing groups afforded moderate
yields. The presence of electron withdrawing groups at
the ortho position showed an adverse effect and did not
furnish any desired products. The mechanism inolves
the quenching of the excited state photocatalyst by
aryldiazonium salt to form an aryl radical with the loss
of N2. The aryl radical then reacts with the olefin of N-
alkyl-N-aryl-2(trifluoromethyl)acrylamides to give rad-
ical intermediate A, which on intramolecular cycliza-
tion followed by SET events affords the desired
product as shown in Figure 1.

2. Addition Reactions
One of the most common reactions of aryl radicals are
the addition to alkenes and alkynes substrates.[17]
Addition to alkenes usually furnish bifuntionalised
molecules such as seleno/thio/aryl/alkyl/keto arenes,[18]
whereas addition to alkynes affords functionalized
ketones and heterocycles.[19] Similarly, domino addi-
tion-cyclization reactions affords functionalized
heterocycles.[20]
In 2012, König’s group reported the photocatalytic
synthesis of benzothiophenes through a radical addi-
tion-annulation process using o-methylthio-diazonium
salts and alkynes (Scheme 2).[21] Following this, many
interesting photocatalytic addition and addition-annula-
tion reactions were reported in the literature, which are
briefly highlighted in the following sub-section.

Scheme 3. Visible light mediated synthesis of functionalized

indoles.

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Figure 1. Proposed mechanism for indole formation.

2.1.2. Synthesis of Isochromenones and Isochroma-

nones

Isochromenone and isochromanone moieties serve as

starting materials for the synthesis of various hetero-
cycles that find application in pharmaceuticals.[23] In
2016, Fagnoni et al. reported their synthesis using a
mild photocatalytic Meerwein type approach. Diazo-
Scheme 4. Photo-catalyzed synthesis of isochromanones &
nium salts derived from anthranilic acid reacts with the Isochromenones.
alkene to form isochromanones with 2 mol% of
Ru(bpy)3Cl2 as photocatalyst under blue light irradi-
ation using acetonitrile as solvent. Substituents on the
alkene as well as on the diazonium salt didn’t change
the outcome of the reaction. Both electron donating as
well as electron withdrawing groups on styrene gave
moderate to good yields. The protocol, when extended
to hydroxyl substituted heteroaromatic compounds;
tricyclic isochromenones were obtained as products
(Scheme 4).[24]
The reaction didn’t furnish any desired product in
the presence of TEMPO, suggesting the involvement
of radical intermediates. The aryl radical generated via
quenching of excited state photocatalyst by aryldiazo-
nium salt reacts with the styrene derivatives resulting Figure 2. Proposed mechanism for isochromanone synthesis.
in a benzylic radical, which then undergoes oxidation
(SET) followed by intramolecular cyclization to afford
isochromanones as shown in Figure 2. At first, the in situ generated aryl radicals undergo
addition with difluoroalkenes to form radical inter-
mediate A, which then reacts with the aryldiazonium
2.1.3. Synthesis of α-Aryl-α,α-Difluroketone
salt to give radical-cation intermediate B. Decomposi-
Cai and co-workers achieved the synthesis of α-aryl- tion of intermediate B results in the formation of
α,α-difluoroketones from α-aryl-β,β-difluoroenol silyls, intermediate C and an aryl radical. Finally, elimination
and arenediazonium salts with a low catalyst loading of trimethylsilyl group from C yields the desired α-
(0.05 mol%) of Ru(bpy)3Cl2 photocatalyst at room aryl-α,α-difluoroketone product (path I). Alternatively,
temperature. Interestingly, few substrates showed sim- the diazonium salt may directly react with the
ilar reactivity under sunlight with 0.01 mol% of the difluorosubstituted alkene via an electrophilic addition
photocatalyst. Both electron withdrawing & neutral reaction to give the desired product (path II). But the
functional groups on the diazonium salts afforded the yield obtained under dark conditions was only 15%,
product in good to excellent yields (Scheme 5).[25]

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SET events lead to the regeneration of the photo-

catalyst and the desired product (Figure 4).

2.1.5. Aryl Alkoxylation of Olefins

In 2018, Yamaguchi et al. synthesized α,β-bifunction-
alized olefins by the reaction of styrenes, diazonium
salts, and alcohols (ROH) with 0.5 mol% Ru(bpy)32 +
as photocatalyst at room temperature. This protocol
gave moderate yields of the product with p-nitro-
benzenediazonium salts whereas other substituents
gave lower yields (Scheme 7).[27] Similarly, α- & β-
Scheme 5. Visible light mediated difluromethylation of arene- substituted olefins also gave the corresponding aryl
diazonium tetrafluroborates. alkoxylation products in moderate yields and with poor
diastereoselectivity (Scheme 8). The aryl radical adds
to the terminal carbon of alkene selectively to form a
suggesting the photoredox cycle to be the dominant secondary or tertiary radical intermediate. Further
pathway (Figure 3). oxidation of this radical intermediate forms a carboca-
tion, which finally reacts with methanol to afford the
desired product (Figure 5).
2.1.4. Synthesis of Polyacrylonitrile
In 2017, Chen et al. used metal-free photoredox
conditions to synthesize polyacrylonitriles with high
molecular weight and low dispersity under mild
conditions in a highly efficient manner. The reaction
involves diazonium salts, acrylonitrile, and eosin Y as
photocatalyst under blue light irradiation with DMF as
solvent (Scheme 6).[26] The aryl radical reacts first with
acrylonitrile and leads to a chain propagation step. In
the end, the F ion from BF4 acts as a chain
terminator to give a radical anion intermediate. Finally,

Figure 4. Mechanism for polyacrylonitrile formation.

Figure 3. Proposed mechanism for difluromethylation of arene-

diazonium tetrafluroborates.

Scheme 6. Synthesis of polyacrylonitrile under metal free Scheme 7. Photoredox catalyzed aryl alkoxylation of terminal
Photoredox conditions. alkenes.

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Scheme 8. Photoredox catalyzed aryl alkoxylation of internal
alkenes.
Figure 5. Mechanism for the formation of aryl alkoxylated
alkenes.
2.1.6. Diarylation of Olefins
In the same year, Li et al. devised a protocol for the
diarylation of alkenes via an intermolecular three-
component reaction involving styrene, diazonium salts,
1,3,5-trimethoxy benzene in the presence of Ir(ppy)3 as
the photocatalyst, under blue light irradiation
(Scheme 9).[28] The reaction follows a Meerwein-type
Scheme 9. Photoredox initiated 1,2 diarylation of alkene with
aryldiazonium salt.
Adv. Synth. Catal. 2021, 363, 1782 – 1809
addition, and the mechanism is similar to the one
proposed by Yamaguchi et al. as shown in Figure 5,
but here instead of the alcohol, trimethoxy-benzene
acts as the nucleophile.
2.1.7. Thio/Selenoarylation of Olefins
In 2019, Maity et al. devised a strategy for synthesiz-
ing organic thio & selenocyanates, which finds wide
applications as bioactive molecules. They achieved the
synthesis via intermolecular aryl thiocyanation of
olefins using diazonium salts and ammonium thiocya-
nate under photoredox conditions. Accordingly, the
reaction of 4-methyl styrene with 4-methoxy-benzene-
diazoniums salts, ammonium thiocyanate, and
Ru(bpy)3(PF6)2 as photo-catalyst furnished the ex-
pected aryl thiocyanated product (Scheme 10).[29] Styr-
ene’s containing electron withdrawing and electron
releasing groups were well tolerated and afforded the
desired products in moderate to good yield.
Similarly, diazonium salts containing different
electron withdrawing and electron releasing groups at
the para position showed good reactivity. In contrast,
substituents in the meta & ortho position resulted in
lower yields. The reaction also worked well on a gram
scale and gave a good yield of the final product. The
method was also successfully applied for aryl seleno-
cyanation of olefins and afforded the desired products
in moderate to good yield (Scheme 11).
2.1.8. Synthesis of Isoflavanones from ortho-Hydrox-
yaryl Enaminone
Iaroshenko et al. developed two different routes for the
synthesis of isoflavonones from ortho-hydroxyaryl
enaminone and aryldiazonium/diaryliodonium salts via
a domino arylation-intramolecular cyclization strategy.
The first methodology involves a photo Meerwein
reaction in which ortho-hydroxyaryl enamienone reacts
with the aryl radical generated from aryldiazonium
salts in the presence of Eosin Y as photocatalyst at
Scheme 10. Photoredox catalyzed intermolecular radical aryl
thiocyanation of alkene.
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Scheme 11. Photoredox catalysed intramolecular radical arylse-
lenocyanation of alkene.
room temperature under green light irradiation. The
other method involves diaryliodonium triflate as an
arylating agent and Ru(bpy)3Cl2 as photocatalyst under
Scheme 12. Eosin Y catalyzed arylation of ortho-hydroxyaryl
enaminone.
Figure 6. Mechanism for isoflavanone synthesis.
Adv. Synth. Catal. 2021, 363, 1782 – 1809
blue light irradiation (Scheme 12).[30] Diazonium salts
containing different functional groups were well
tolerated and the same was the case with substituted
ortho-hydroxy enaminenone. The aryl radicals gener-
ated via oxidative quenching of excited photocatalyst
react with ortho-hydroxyaryl enaminenone to give α-
amino radical intermediate (A). Intermediate A then
oxidizes to iminium ion (B), followed by intramolecu-
lar cyclization and elimination of dimethylamine to
afford the desired products, as shown in Figure 6.
2.2. Addition to Alkynes
2.2.1. Chemoselective Radical Addition/Oxidation
Domino Process
Alkynes undergo ‘Atom Transfer Radical Addition’
(ATRA)[31] to give α,α-difunctionalized aryl ketones.
Niu and co-workers synthesized α,α-difunctionalized
carbonyls from aryldiazonium salt and alkynes via
photoredox catalysis. The reaction of aryldiazonium
salt with the photocatalyst (Eosin Y or Ru(bpy)32 +)
generates an aryl radical, which triggers a chemo-
selective domino reaction to give α-chloro or α-alkoxy
aryl ketones with NaCl or ROH & O2 respectively in
good to moderate yields (Scheme 13).[32]
When diazonium salts containing electron with-
drawing groups were used, the reaction gave higher
yields with eosin Y as photocatalyst. Similarly,
diazonium salts containing electron releasing groups,
gave better yields with Ru(bpy)32 +. The mechanism
involves the addition of aryl radical to the alkyne
followed by oxidation and nucleophilic substitution
leading to the formation of the final product, as shown
in Figure 7.
2.2.2. Synthesis of Indole Derivatives from Alkynes
Although functionalized indoles’ synthesis via alkene
addition was reported,[33] synthesis of difuctionalized
indoles from alkynes under mild conditions was
challenging. Jin et al. achieved the synthesis of 2,3-
disubstituted indoles using photoredox catalysis from
alkynes and aryl diazonium salts. The reaction of o-
Scheme 13. Chemoselective radical addition/oxidation domino
process.
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arylations were achieved using aryldiazonium salts as

the aryl source under mild and green conditions.[36]
More than three decades after the Deronzier’s synthesis
of phenanthrene using aryldiazonium salts, Stanford
reported a ligand directed C H arylation using dual
palladium-photoredox catalysis with aryldiazonium
salts (Scheme 15).[37] The method was compatible with
a variety of directing groups such as amides, oximes
and pyrimidines, pyridine, etc. Following this, König’s
group achieved direct C H arylation of heteroarenes
using eosin Y and visible light with aryl diazonium
salts.[36]

3.1. Arylation of Anilides using Aryldiazonium

Figure 7. Mechanism for radical addition/oxidation domino
process.
Salts
In 2017, Balaraman and co-workers reported ortho-
C H arylation of anilides in excellent yields under
green conditions using eosin Y as photocatalyst and
Pd(OAc)2 as the transition metal catalyst with MeOH
as solvent (Scheme 16).[38] In the same year, Xu and
co-workers also reported the synthesis of ortho-
arylated acetanilides and benzamides (Scheme 17) by

azido aryl alkynes, aryl diazonium salts, and 1,4-CHD

(cyclohexadiene) with Eosin Y as photocatalyst and
acetonitrile as a solvent under 5 W blue LED irradi-
ation furnished difuctionalized indoles (Scheme 14).[34]
Both electron withdrawing and electron releasing
groups on the terminal alkynes were well tolerated and
afforded the product in moderate yields.

3. Direct C H Arylation
Direct C H arylation is an attractive alternative for the
traditional cross coupling reaction (Heck, Suzuki and
Sonogashira etc.) which are widely developed and Scheme 15. Photocatalyzed C H arylation.
studied.[35] However the growing desire for mild and
green methods demands an alternative route for
achieving this ubiquitous transformation. Since the
past decade, photoredox catalysis has attracted much
attention from synthetic chemists for achieving various
C H functionalizations and in this direction C H

Scheme 14. Substituted indole formation via Photoredox catal- Scheme 16. Dual Pd(II)/Eosin Y catalysed arylation of anilides
ysis. using aryldiazonium salts.

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by the photocatalyst oxidized form, PC + to form the

*

ground state photocatalyst, PC. Reductive elimination

of Pd(IV) intermediate finally affords the desired C H
arylated product and regenerates the Pd(II) catalyst for
further catalytic cycles (Figure 8).

3.3. C H arylation of (Hetero)Arenes

Scheme 17. C H arylation of acetanilides and benzamides.
merging palladium catalysis with organophotoredox
(9,10-dihydroacridine as photocatalyst) catalysis.[39]
3.2. Arylation of Simple Phenylureas
Recently, our group reported the chemoselective C H
arylation of free phenylureas with aryldiazonium salts
at room temperature using a dual catalytic pathway.
This methodology works efficiently for simple phenyl-
In 2017, Xu and co-workers reported direct C H
arylation of heteroarenes using aryldiazonium salts
without any directing groups. The reaction proceeds at
room temperature with AcrH2 A as photocatalyst
under blue light irradiation. C-2 arylation of five-
membered heterocycles such as pyrrole, furan, and
thiophene was demonstrated along with the synthesis
of biaryl products but with ten equiv. of benzene
(Scheme 19).[41]
They proposed an oxidative quenching cycle sim-
ilar to Deronzier’s report except for the last step. They
suggested two possible pathways for the final step: (a)
conventional oxidation by PC + and (b) oxidation by
*

ureas and also for di, tri and tetra- substituted phenyl-
ureas. Since phenylureas containing electron with-
drawing groups were not suitable for the
transformation, we took it as an advantage to acheive
regioselective arylation on N,N-diphenylureas by a
careful choice of the starting materials. Its noteworthy
to mention that we achieved both symmetrical and
unsymmetrical diarylation reactions using the same
catalytic system but with varying catalyst loading
(Scheme 18).[40]
In all these cases, the palladacycle intermediate
resulting from the initial C H bond activation was
intercepted by the aryl radical generated from the
photocycle to give a Pd(III) intermediate. The Pd(III)
intermediate is further oxidized to Pd(IV) intermediate

Figure 8. Mechanism for dual catalytic C H arylation.

Scheme 19. C H arylation of (hetero)arenes with aryldiazo-

Scheme 18. C H arylation of phenylurea. nium salts.

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aryldiazonium salt leading to a chain reaction (autoca-
talyzed) (Figure 9).
3.4. C H Arylation of Heteroarenes and Coumarins
In the same year, Gryko and co-workers reported direct
C H arylation of heteroarenes and coumarins using a
porphyrin photocatalyst under blue light irradiation at
room temperature. Interestingly, these reactions are not
sensitive to the steric substituents on the diazonium
salts but sensitive to electronic factors. Electron-donor
substituted diazonium salts were less reactive than
electron acceptor substituted aryldiazonium salts.
Notably, N-methyl indole and N-methyl pyrrole were
Figure 9. Proposed mechanism for C H arylation of (hetero)
arenes.
Scheme 20. Porphyrin catalyzed C H arylation of heteroarenes/
coumarins.
Adv. Synth. Catal. 2021, 363, 1782 – 1809
not suitable substrates for this transformation as they
directly quenched the excited state photocatalyst
(Scheme 20).[42]
3.5. C H Arylation of (Hetero)Arenes under Sun-
light
Yijin Rao and co-workers explored the photocatalytic
behaviour of naturally occurring perylenequinonoid
pigment, cercosporin. By employing this photocatalyst
they reported C H arylation of benzenes, heteroarenes
(furan, thiophene, N-Bocpyrrole, pyridines, and pyr-
imidines) and fused heteroarenes (quinolones, benzox-
azoles, and benzthioxazoles) at room temperature with
sunlight as the light source. Notably, they also
successfully achieved C H arylation of electron-poor
N-Boc pyrroles in high yields (Scheme 21).[43]
3.6. C H Arylation with Anilines via in situ
Generated Diazonium Salts
In 2018, Cai and co-workers achieved C H arylation
of heteroarenes by merging visible light photoredox
catalysis with micellar catalysis using eosin B as
photocatalyst and Triton X-100 as the surfactant
(Scheme 22).[44] Aryldiazonium salt was generated
in situ from aryl amines and t-BuONO at room temper-
ature. More importantly, water was used as the solvent
for this transformation. Along with the direct C H
arylation of heteroarenes, the authors also achieved the
synthesis of sulfide & selenide-substituted phenan-
threnes (Scheme 23), and α-arylated ketones from enol
acetates.[18d] Anilines containing electron-withdrawing
and neutral substituents gave high yields relative to
anilines containing electron-donating groups.
Scheme 21. C H arylation of (hetero)arenes under sunlight.
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Scheme 24. Heterogeneous photoredox arylation with aniline.

Scheme 22. C H arylation using anilines via in situ generated

diazonium salts. photocatalyst.[46] The reaction proceeds smoothly with
both electron-donating and electron-withdrawing sub-
stituents on the aryldiazonium salts, whereas lower
yields were obtained for anilines containing electron-
withdrawing groups. Para substituted N,N-dialkylated
anilines gave the desired C H arylation product in
good yields, but other derivatives such as ortho/meta
Scheme 23. Synthesis of phenanthrene.
substituted and unsubstituted anilines gave mixture of
isomers. Similarly, N-mono alkylated, and free anilines
were not suitable for this transformation (Scheme 25).
3.7. Heterogeneous Photoredox Arylation with Ani-
line
Recently, heterogeneous photoredox arylations have
drawn much attention since the photocatalyst is
generally not recovered or reused. In 2018, Mingyang
He and co-workers developed visible light-mediated
C H arylations using PANI-g-C3N4 TiO2 composite as
the heterogeneous photocatalyst (Scheme 24).[45] Direct
C H arylation of heteroarenes & benzoquinones was
achieved using aniline as the aryl partner (via in situ
diazotization). In all these cases, arylation occurred at
the most acidic alpha-position in heteroarenes (furan,
thiophene, N-Bocpyrrole). They also applied this
strategy for the synthesis of α-arylated ketones via α-
arylation of enol acetates. The photocatalyst was
reused for almost 10 cycles, with only a slight decrease
in the yield from the first cycle (87–79%).

3.8. Metal-Free direct C H Arylation of Aniline

In 2019, Yadav and co-workers reported the synthesis
of 2-amino biphenyls via direct C H arylation of
anilines with aryldiazonium salts under metal-free
conditions using an organic dye (eosin Y) as the Scheme 25. Metal-free direct C H arylation of aniline.

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3.9. Metal-Free Intramolecular C H Arylation

Feng and co-workers used an intramolecular C H

arylation strategy to synthesis 6H-benzo[c]chromenes
from aryl diazonium salts by employing eosin Y as the
photocatalyst under green light irradiation. It is an
attractive alternative for the synthesis of 6H-benzo[c]
chromene using metal photocatalysts commonly em-
ployed for Pschorr reactions (Scheme 26).[47]
The authors also demonstrated the same reaction
starting from the corresponding anilines via in situ
diazotization with t-BuONO. Both electron donating
and electron withdrawing substituents on the aryldia-
zonium salts gave good yields of the final product.
Similarly for meta-substituted benzyl systems, two
different regioisomers were obtained.
Scheme 27. Metal-free direct C H arylation of 2H-indazoles
with aryldiazonium salts.
3.10. Metal-Free Direct C H Arylation of 2H-
Indazoles
Dong-Pyo Kim and co-workers demonstrated direct 3.11. Metal-Free Direct C H Arylation of Quinox-
C H arylation of 2H-indazoles at C-3 position with alin-2(1H)-One
aryldiazonium salts using eosin Y as the photocatalyst
at room temperature.[48] By using a continuous flow Metal-free direct C H arylation of Quinoxalin-2(1H)-
process, the reaction time was reduced to 1 min. N-2- one was recently demonstrated by Kim and others
phenyl-substituted 2H-indazoles afforded good yields, using eosin Y photocatalyst under blue light irradi-
whereas N-2- alkyl, benzyl, heteroaryl substituents ation. This method is applicable for a wide variety of
didn’t furnish the desired products. The authors Quinoxalin-2(1H)-ones and aryldiazonium salts result-
proposed a reductive quenching pathway, wherein ing in moderate to high yields of C-3 arylated products
DIPEA first quenches the excited state photocatalyst, (Scheme 28).[49]
PC to form PC . Aryl radicals are then generated via
*

SET between aryldiazonium salts and the reduced

3.12. Visible-Light Induced Self-Promoted Aryla-
photocatalyst, PC . The aryl radicals then add to 2H-
*

indazoles, followed by oxidation and rearomatization,
affords the desired product. Using this protocol, the
authors achieved the synthesis of few drug derivatives
used for the treatment of cardiovascular disease in a
single step in high yields (Scheme 27).
tion of BODIPYs
In 2019, Wang et al. achieved C H α-arylation of
BODIPYs with aryldiazonium salts in the absence of
any external photocatalyst or additives. The photo-
catalytic behavior of BODIPY’s under visible light
drives this reaction. Monoarylation was achieved using
1.2 equiv. of aryldiazonium salt and with 1 W

Scheme 26. Intramolecular C H arylation for the synthesis of Scheme 28. Metal-free direct C H arylation of Quinoxalin-
6H-benzo[c]chromene. 2(1H)-one.

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Scheme 29. Photoredox self-catalysed regioselective arylation
of BODIPYs.
Figure 10. Proposed mechanism for the arylation of BODIPYs.
Scheme 30. Photocatalyst free photoarylation of pyridines with
aryldiazonium salts via EDA approach.
Adv. Synth. Catal. 2021, 363, 1782 – 1809
(450 nm) LEDs whereas 3,5 diarylation was achieved
with 4 equiv. of aryldiazonium salt under 10 W
(450 nm) LED irradiation (Scheme 29).[50] Singlet
excited BODIPY acts as the photo-reductant upon
irradiation with visible light, which leads to the
formation of aryl radical. The aryl radical then
immediately adds to BODIPY followed by oxidation
and elimination affords the desired arylated product
(Figure 10).
3.13. Direct C H Arylation of Pyridines
In 2019, Bartolomeu et al. reported direct C H
arylation of pyridines without any photocatalyst using
an electron donor-acceptor (EDA) approach under
visible light irradiation (Scheme 30).[51] At first, the
aryldiazonium salt forms an adduct with pyridine to
form the EDA complex. The EDA complex on
absorbing the visible light goes to the excited state,
which immediately dissociates to form aryl radicals.
The aryl radical further reacts with pyridinium salt
leading to the formation of new radical species, A.
Subsequent oxidation by oxygen followed by rear-
omatization leads to the desired product (Figure 11).
It’s noteworthy to mention that this reaction
proceeds smoothly with water as the solvent. The
reaction yields a mixture of isomers when simple
pyridines are employed. The reaction is compatible
with different substituted pyridines, quinolines, and
quinoxalines. Similarly, the reaction works smoothly
with both electron donor and neutral substituted
diazonium salts. On the other hand, electron acceptor
substituted diazonium salts are not suitable substrates
for this transformation.
Figure 11. Proposed mechanism for the photoarylation of
pyridines via EDA complex.
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3.14. C H arylation of Xanthines with Aryl Azosul-
fones
In 2019, Fagnoni and co-workers established a proto-
col for the C H arylation of xanthines with aryl
azosulfones without any external photocatalyst.[52] The
reaction proceeds smoothly under both sunlight (in a
flow reactor) and blue light irradiation (in pyrex
vessel). Mild to strong acids (HCOOH or HCl) were
employed for xanthine’s solubility since it precipitated
during the reaction. The reaction almost gave similar
yields for both batch and flow reactions (Scheme 31).
Aryl azosulfone on irradiation with visible light goes
to singlet excited state, which then undergoes homol-
ysis to form an aryl and sulfonyl radical. The aryl
radical then adds to the C-8 position of xanthine,
which on further oxidation followed by rearomatiza-
tion affords the desired C H arylated product (Fig-
ure 12).
4. Dual Gold-Photoredox Catalysis
4.1. α-Aryl Enones from Propargyl Alcohols
Although homogeneous gold catalysis is well studied
over the past two decades, after the seminal reports of
Glorius et al. on oxy- and amino-arylation reactions in
Scheme 31. Metal-free direct C H arylation of xanthines.
Figure 12. Possible mechanism for C H arylation of xanthines.
Adv. Synth. Catal. 2021, 363, 1782 – 1809
2013 by merging gold catalysis with photoredox
catalysis; dual gold-photoredox catalysis has begun to
find a wide variety of applications in organic
synthesis.[53] Shin’s group in 2016 used a dual gold-
photoredox catalytic approach for the synthesis of α-
aryl enones from propargyl alcohols with aryldiazo-
nium salts via Meyer-Schuster rearrangement
(Scheme 32a).[54] This reaction proceeds smoothly with
Ph3PAuCl and Ru(bpy)3(PF6)2 catalysts under blue
LED irradiation. In the same year, Alcaide et al.
utilized a similar approach to synthesize α-aryl enones
but with better diastereoselectivity using Ph3PAuNTf2
as the catalyst (Scheme 32b).[55]
In both cases, the mechanism is believed to proceed
via the aryl Au(III) cationic complex, formed via
photoredox mediated oxidative addition of aryldiazo-
nium salt to Au(I) neutral complex. The cationic
complex then activates the propargyl alcohol to give
intermediate A, which on 1,3-hydroxide (hydroper-
oxide) transposition forms allene intermediate B.
Intermediate B on hydrolysis followed by dehydration
or methanol elimination, gives a vinyl-Au(III) inter-
mediate. Finally reductive elimination of vinyl-Au(III)
intermediate affords the desired product as shown in
Figure 13.
Scheme 32. α-aryl enones via dual gold-photoredox catalysis.
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transmetallation followed by reductive elimination,

forms aryl terminated alkynol which is a starting
material for the second catalytic cycle and follows a
similar mechanism as discussed above (Figure 14).

4.3. Oxy-Arylation of Alkynes for the Synthesis of

Benzofuran
Later in the same year, Fensterbank and co-workers
developed a powerful method for synthesizing 3-
arylbenzofuran from o-alkynylphenols with aryldiazo-
nium salts via oxy-arylation of alkynes under mild
conditions by employing a dual gold-photoredox
catalysis (Scheme 34).[57] Cationic Au(III) complex
formed via oxidative addition of aryl diazonium reacts
with o-alkynylphenols and undergoes cyclization via
Figure 13. Mechanism for the synthesis of α-aryl enones. an intramolecular nucleophilic attack. Reductive elim-
ination then affords the desired benzofuran in good
yields. The reaction works smoothly with both electron
4.2. α-Aryl Enones from TMS-Terminated Alkynols donating and electron withdrawing substituents on the
aryldiazonium salts.
In the successive year, Alcaide et al. developed another
interesting protocol for the synthesis of α-aryl enones
from TMS-alkynols and aryldiazonium salts by em-
ploying a dual gold-photoredox catalyzed double
arylation strategy (Scheme 33).[56] They applied this
protocol for the oxy arylation of alkynes to get the
desired diarylated benzofuran. In the first cycle, aryl
terminated alkynol was generated from TMS-termi-
nated alkynols via dual gold-photoredox catalysis. The
aryl Au(III) cationic complex formed via photoredox
mediated oxidative addition (aryl radical addition to
Au(I) followed by SET from A to PC +) of aryldiazo-
*

nium salt to Au(I) neutral complex, binds with TMS-

alkynols, 1 to form intermediate B. Intermediate B on

Figure 14. Proposed mechanism for the synthesis of aryl

terminated alkynols.

Scheme 33. Synthesis of α-aryl enones from TMS-terminated Scheme 34. Oxy-arylation of alkynes for the synthesis of
alkynols. benzofuran.

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4.4. Synthesis of Indoles via Amino-Arylation of
Alkynes
Zhu and co-workers reported another interesting
method for the synthesis of indoles through amino-
arylation of alkynes with aryldiazonium salts under
mild conditions by using dual gold and photoredox
catalysis at room temperature with 33 W CFL light.
They employed o-alkynyl-N-protected anilines as
starting material. Notably, this method gives access to
multi-substituted indoles in high yields (Scheme 35).[58]
4.5. Synthesis of Biaryls and 2-Arylbenzofuran
In 2018, Patil and co-workers revealed an interesting
report for the synthesis of biaryls and 2-arylbenzofuran
through cross-coupling of (hetero)arylsilanes with
aryldiazonium salts. The authors investigated several
Scheme 35. Oxy-arylation of alkynes for the synthesis of
benzofuran.
Scheme 36. Dual gold-photoredox mediated synthesis of biaryls
and 2-arylbenzofuran.
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catalytic combinations and finally succeeded with a
combination of copper, gold, and ruthenium (photo-
redox catalyst) tri-catalytic system (Scheme 36).[59]
The reaction works smoothly with both electron
donating and withdrawing substituents on aryldiazo-
nium salts. In the case of silanes, (hetero)arylsilanes
such as 3-methyl-2-trimethylsilyl-benzofuran, 2-
trimethylsilyl benzothiophene, and N-protected-2-
trimethylsilyl indoles works smoothly and affords the
resultant products in 69%, 65%, and 59%, respectively.
The mechanism follows a similar cycle involving an
Au(III) intermediate. The Au (III) intermediate under-
goes transmetalation with the aryl-copper species
generated in situ by transmetalation of aryl silanes and
the Cu(I) catalyst and results in diarylated Au(III)
intermediate. Finally, reductive elimination of the
Au(III) intermediate affords the desired product in
good yields (Figure 15).
5. Cross-Coupling Reactions
5.1. Alkynylation of Arene Diazonium Salts with
Alkynyl Carboxylic Acids
The noble prize-winning work by Heck, Suzuki, and
Sonagashira et al. on cross-coupling reactions have
enticed much attention. Even though these methods are
well established, drawbacks such as the requirement of
prefunctionalized starting materials, elevated temper-
atures, unambiguous ligand, and additives demand
mild and alternative methods. Therefore many cross-
coupling arylation reactions mediated by visible light
photoredox catalysis have been developed over the
past decade. In 2019, Yang et al. reported a syntheti-
cally viable method for the preparation of diaryl
alkynes under metal-free photoredox conditions with
aryldiazonium salts. Notably, the authors used an
Figure 15. Possible mechanism for the synthesis of biaryls and
2-arylbenzofuran.
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organic dye (eosin Y) as photocatalyst, acetoxybenzio-
doxole as additive, and stable alkyne carboxylic acids
as the reacting partner under green light irradiationat
room temperature. The reaction worked smoothly,
irrespective of electronic and steric factors
(Scheme 37).[60]
5.2. Cross-Coupling of Aryldiazonium and Sulfinate
Salts
Sulfones are important structural motifs present in
many pharmaceutical and agrochemical molecules.
Although there are several methods for their synthesis,
there is still a requirement for a robust protocol.
Chawla et al., in 2019, achieved this via cross-coupling
of aryldiazonium and sulfinate salts using metal-free
photoredox catalysis (Scheme 38).[61] Notably, this
method gave access to the synthesis of a variety of
aryl/alkyl sulfones at room temperature with no metal
catalyst under mild conditions. The authors proposed,
the aryl radical formed from excited state PC* via SET
and the sulfonyl radical generated by the reduction of
Scheme 37. Metal freephotoredox alkynylation with alkynyl
carboxylic acids.
Scheme 38. Synthesis of sulfones via cross-coupling of aryldia-
zonium and sulfinate salts.
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PC + to PC by sulfinate salts, coupled to form the
*
desired product in good yield (Figure 16).
5.3. Synthesis of Biaryls
Fouquet et al. reported a dual gold-photoredox cata-
lyzed cross-coupling of aryldiazonium salts with aryl
boronic acids by using 9-mesityl-10-acridinium tetra-
fluoroborate (4 mol%) and Ru(bpy)3(PF6)2 (2 mol%)
photocatalyst to afford biaryls (Scheme 39).[62] The
mechanism is believed to proceed via an aryl-gold
complex, A resulting from transmetallation of Au(I)
catalyst with aryl boronic acids. Au(I) complex, A
undergoes oxidation with the aryl radicals generated
from the photocatalytic cycle to form Au(II) species B.
Further oxidation of intermediate B by PC + or by the
*
diazonium salt results in Au(III) intermediate, C.
Finally, reductive elimination of Au(III) complex
affords the desired biaryl product and regenerates
Au(I) catalyst (Figure 17).
5.4. Cross-Coupling of Aryl Silanes
In 2018, Hashmi et al. achieved the synthesis of biaryls
and diaryl alkynes from aryldiazonium salts via cross-
coupling with aryl silanes or borates without any
photosensitizer and by using gold catalyst under visible
Figure 16. Possible mechanism for cross-coupling of aryldiazo-
nium salts with sulfones.
Scheme 39. Dual gold and photoredox approach for the syn-
thesis of biaryls.
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Figure 17. Possible mechanism for the synthesis of biaryls.
light irradiation at room temperature. The reaction
proceeds through an Au(III) intermediate formed via
formal oxidative addition of aryldiazonium salt to
Au(I) complex, which then undergoes transmetalation
(with alkynylsilanes or aryl borates or sillica(tes)nes)
followed by reductive elimination to afford the desired
products (Scheme 40).[63]
6. C N Bond Formation
6.1. Synthesis of Aryl-Azoimidazo-Heteroarenes
Sumbal Saba et al. reported the synthesis of aryl-
azoimidazo-heteroarenes in good to excellent yields
under mild conditions using Na2EosinY as photo-
catalyst, MeCN as solvent at room temperature
(Scheme 41a).[64] This protocol was extended for the
gram-scale synthesis of biologically relevant aryl-
azoimidazo-heteroarenes from aryl diazonium tetra-
fluoroborate via C(sp2) H functionalization.[65] This
method was further exploited to synthesize diazo
Scheme 40. Photocatalyst free synthesis of biaryls and diary-
lalkynes.
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asc.wiley-vch.de
Scheme 41. a) EosinY catalysed C N formation of heteroar-
enes using aryldiazonium salt. 41. b) Eosin catalyzed C N
formation of anilines with aryldiazonium salt.
substituted aniline derivatives from the corresponding
anilines and aryldiazonium salts (Scheme 41b).
The methodology’s significant aspect was easy
access to free amines from diazo compounds on
reduction with zinc and acetic acid. These free amines
are useful building blocks for complex organic and
biological compounds (Scheme 42).[66]
The authors proposed two possible mechanistic
pathways; one involving an ionic path and the other a
radical path as shown in Figure 18. In the ionic course,
the imidazole heteroarenes react directly with the
aryldiazonium salts to give an azo-carbocation species,
which further undergoes deprotonation to produce the
desired product A. In the radical pathway, the excited
photocatalyst, EY* produces an aryl radical via single
electron transfer (SET) to diazonium salts. This further
Scheme 42. Access toimidazo [1,2-a]pyridin-3-amines from azo
imidazole arenes.
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Figure 18. Proposed mechanism for azo coupled arenes.
couples with heteroarenes to produce an azo radical
species, which on SET with EY + . produces an azo
cation while regenerating the catalyst. Finally, the azo
cation on deprotonation results in the expected product.
All electron withdrawing groups ( Br, NO2,
COMe), electron donating groups ( OMe, OCH2O),
and sterically hindered phenyl substituents afforded the
corresponding azo-coupled product in good to excel-
lent yields.
6.2. Azo-Trifluoromethylation of Alkenes with Ar-
yldiazonium Salts and Sodium Triflinate
Xing-Long Yu et al. reported azo trifluoromethylation
of alkenes via a three-component reaction involving
olefin, aryldiazonium salts, and sodiumtriflinate (Lan-
glois reagent) using Ru(bpy)3 as the photocatalyst
(PC). Olefins containing electron-withdrawing and
electron-donating groups were utilized as substrates to
produce an azo-trifluoromethylated product in good to
excellent yields (69–86%). Functional groups such as
ester, TMS, phenyl ether, and hydroxy substituents
were also well-tolerated and gave the resultant prod-
ucts in moderate to excellent yields. Several disubsti-
tuted, linear, and cyclic olefins also afforded the final
products in good yields (Scheme 43).[67]
6.3. Photoredox-Catalyzed Synthesis of Alkylaryl-
diazenes
Angnes et al. achieved the synthesis of alkyl-aryl
diazenes from substituted dihydropyridines (DHP’s)
Adv. Synth. Catal. 2021, 363, 1782 – 1809
Scheme 43. Azo-trifluoromethylation of alkenes.
and aryldiazonium salts under photocatalytic
conditions.[68] Aryldiazonium salts containing both
electron donating and withdrawing substituents such as
methoxy, trifluoromethyl, cyano, methylenedioxy, and
acetyl groups were well tolerated under the conditions
to give the resultant products in good yields. Further-
more, complex diazonium salts containing biphenyl,
naphthalene, benzophenone, and coumarin substituents
also successfully afforded the desired products in good
yields. A wide variety of DHPs, containing free
alcohol, ester, and Boc-protected amines undergoes
C N bond formation in good yields. When DHPs
containing heteroaromatic rings like quinoline, thia-
zole, thiophene, pyridine, oxazole, and indole were
used as substrates, the final products were obtained in
low yields (Scheme 44a & b). Notably, the significance
of diazene compounds was demonstrated by synthesiz-
ing indole derivatives under mild conditions via
Fischer indole synthesis.
The mechanism involves the reduction of catalytic
amount of diazonium salt, B to the corresponding aryl
radical, F by excited photocatalyst. The aryl radical
(F) then generates an alkyl radical (R ) and pyridine
*
derivative, E, from the substituted DHP via a hydrogen
atom abstraction. Alternatively, the same alkyl radical
(R ) could also be generated via oxidation of A by
*
PC +. The alkyl radical then reacts with the aryldiazo-
*
nium salt (B) to result in a nitrogen centered cationic-
radical intermediate, D. This is further reduced to
diazenes, C either by the excited photocatalyst via SET
or by another DHP molecule as shown in Figure 19.
6.4. Synthesis of N-Arylamides
Anil. K. Singh et al. reported the synthesis of N-
arylamides from aryl diazonium salts with nitriles
under metal-free conditions by using an organic dye
(eosin Y) as photocatalyst via a Ritter type intermedi-
ate and using water as the solvent. The reaction
proceeded smoothly with various aryldiazonium salts
containing electron donating, and electron withdrawing
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Scheme 44. a) Synthesis of alkyl-aryldiazene. b) Synthesis of
alkyl-aryldiazene from 4-methyl diazonium salts.
Figure 19. Proposed catalytic cycle for the formation of alkyl-
aryldiazenes.
substituents to afford N-arylamides in good to ex-
cellent yields. Surprisingly, heterocyclic diazonium
salts containing electron-withdrawing groups such as
Cl, F substituent gave the final products in lower yield
when compared to other functional groups
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(Scheme 45).[69] The mechanism involves the reaction
of the aryl radical with alkyl nitriles to result in an
imine radical, which undergoes oxidation followed by
nucleophilic substitution with water to render the
desired product.
7. C S Bond Formation
7.1. Synthesis of β-Sulfonated Ketone
Fu-Sheng and co-workers investigated the synthesis of
β-sulfonated ketones via a three-component multi-
component reaction (MCR) involving alkenyl cyclo-
butanol, DABCO · (SO2)2, and aryldiazonium salt using
fac-Ir(ppy)3 as the photocatalyst under blue light
irradiation. Alkenyl cyclobutanols containing electron
donating & electron withdrawing groups on the
aromatic rings under standard reaction conditions
affords the desired products in good yields
(Scheme 46).[70]
The authors proposed the mechanism as shown in
Figure 20.[71] At first, the aryl sulfonyl radical, gener-
ated from aryldiazonium salt and DABCO · (SO2)2,
reacts with the olefin of alkenyl cyclobutanol to
provide a radical intermediate, which is further
oxidized by the photocatalyst to form a cationic
intermediate. Further, deprotonation by DABCO and
subsequent semipinacol rearrangement provided the
desired product.
7.2. Synthesis of Sulfonated Thiols from Aryl
Diazonium Salts
Akshay M. Nair and co-workers investigated aryl
sulfonylation of thiols by treating thiophenol &
DABCO · (SO2)2 with aryl diazonium salt at room
Scheme 45. Synthesis of N-arylamide from diazonium salt.
Scheme 46. Synthesis of β-sulfonated ketone.
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Figure 20. Proposed mechanism for the formation of β-sulfo-
nated ketones.
temperature under photocatalytic conditions using
eosin Y as a photocatalyst (Scheme 47).[72] Thiophenols
bearing various functional groups such as methyl,
methoxy, isopropyl, halogens, and naphthalene fur-
nished the desired products in good yields under the
optimized conditions. Notably, aliphatic thiols were
also effective for this transformation and gave the
expected products in good yields. More interestingly,
tetra acetylated thio glucose, when employed as the
substrate, afforded the glycosylated thiosulfonate in
high yield, which was used as the precursor for
glycoprotein synthesis. Subsequently, the authors also
expanded the scope of the protocol with various
aryldiazonium salts containing both electron donating
and electron withdrawing substituents. The reaction
worked efficiently with electron donating substituents,
while electron-deficient nitro substituent gave rela-
tively lower yields.
Scheme 47. C S Sulfonylation of aryl diazonium salts.
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7.3. Synthesis of Arenesulfonyl Chlorides
Arenesulfonyl chlorides were synthesized from in situ
generated aryldiazonium salts (from anilines), sulfonyl
chloride, and Ru(bpy)3Cl2 as the photoredox catalyst
under mild conditions by Michal Majek and co-work-
ers (Scheme 48).[73] More importantly, water was used
as a solvent for this reaction. Arenediazonium salts
bearing functional groups such as halo, azido, ester,
nitro & -CF3 efficiently worked under the reaction
conditions to give high yields of the desired products.
2-nitro-benzenesulfonyl chloride gave a lower yield
and was attributed to the side reaction between
deactivated 2-nitro aniline and nitrosonium ion. The
generated aryl radical was quickly trapped by SO2 to
form the S-centered sulfonyl radical. Subsequently, the
sulfonyl radical reacts with the chloride anion to
furnish arenesulfonyl chloride via electron transfer to
the oxidized form of the photocatalyst, [Ru(bpy)3]3 +
resulting in the regeneration of ground-state photo-
catalyst (Figure 21).[74]
7.4. Synthesis of Sulfonated Isobenzofuran-1(3H)-
Ones through Aryldiazonium Salts
Jun Zhang and co-workers reported the synthesis of
sulfonated isobenzofuran-1(3H)-ones starting from 2-
vinyl benzoic acids, aryldiazonium salts, DAB-
CO · (SO2)2 and Ir(ppy)3 as the photocatalyst under
Scheme 48. C S bond formation for the synthesis of arenesul-
fonyl chloride.
Figure 21. Mechanism for the synthesis of arenesulfonyl
chloride.
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visible light at room temperature (Scheme 49).[75] A
variety of aryl diazonium salts were utilized to obtain
the desired products in good yields. Similarly, vinyl
benzoic acid derivatives bearing different substituents
worked efficiently under these conditions to afford the
expected sulfonated isobenzofuran-1(3H)-ones in ex-
cellent yields. At first, the aryl sulfonyl radicals,
generated from aryl diazonium salts & DABCO · (SO2)2
react with the double bond of the vinyl group leading
to a radical intermediate. In the photoredox cycle,
Ir(III) catalyst on irradiation with light forms excited
Ir(III)*, which reduces the cationic amine radical to
form DABCO & Ir(IV). The previously generated
radical intermediate then undergoes SET with Ir(IV) to
form the ground state photocatalyst and a cation
intermediate. DABCO then acts as a base and
promotes an intramolecular nucleophilic cyclization of
carboxylic acid to furnish the sulfonated isobenzofur-
an-1(3H)-one (Figure 22).
Scheme 49. Synthesis of sulfonated isobenzofuran-1(3H)-ones.
Figure 22. Proposed mechanism for the synthesis of sulfonated
isobenzofuran-1(3H)-ones.
Adv. Synth. Catal. 2021, 363, 1782 – 1809
7.5. Synthesis of Aryl Sulfides from Aryldiazonium
Salts
Visible-light mediated coupling of thiols with aryldia-
zonium salts was demonstrated by Jia Li et al. Aryl
thiols containing methyl, tert.butyl, -Cl, and -Br
substituents on the phenyl ring were treated with
various aryldiazonium salts under metal-free photo-
catalytic conditions to give the expected products in
average to excellent yields. Furthermore, aryldiazo-
nium salts bearing electron donating and electron
withdrawing substituents afforded the desired aryl
sulfides in good yields (Scheme 50).[76] Cercosporin
(CP), synthesized from liquid fermentation of glucose,
was used as the photocatalyst for this
transformation.[77]
Excited photocatalyst, CP* acts as a reductant to
form aryl radicals from aryldiazonium salts. Thiol then
reduces the oxidized photocatalyst to form ground state
cercosporin, CP, and thiol radical cation. Finally,
deprotonation of thiol radical cation forms thiol
radical, which couples with the aryl radical to furnish
the desired diaryl sulfide in good yields (Figure 23).
7.6. Chemoselective Synthesis of Diaryldisulfides
from Coupling of Arenediazonium Salts
In 2017, Jing Leng et al. achieved the synthesis of aryl
disulfides from aryldiazonium salts and CS2 with
Scheme 50. Synthesis of Aryl sulfides from aryldiazonium
salts.
Figure 23. Proposed mechanism for thioarylation.
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Ru(bpy)3(PF6)2 photocatalyst. The scope of aryl diazo-
nium salts bearing electron donating and electron
withdrawing groups were successfully demonstrated,
and the desired aryl disulfides were obtained in 42–
90%. Furthermore, sterically hindered substrates gave
the desired products in good yields and functional
groups such as -Cl, -Br, ester, methyl, nitro, and phenyl
were also compatible under the reaction conditions
(Scheme 51).[78]
Aryl radicals generated from aryldiazonium salts
add to the sulfur of CS2 to provide a carbon-centered
radical intermediate.[79] This intermediate then forms
an aryl sulfide radical through cleavage of carbon-
sulfur bond by releasing carbon sulfide.[80] The aryl
sulfide radical then undergoes a further transformation
in three different ways, as shown in Figure 24, to form
the corresponding diaryl disulfides.
7.7. Synthesis of S-Aryl Thiosulfonates
In 2019, Xinxing Gong and coworkers explored the
synthesis of aryl S-thiosulfonate from aryldiazonium
salts using thiourea and sodium metabisulfite in the
presence of an organic photocatalyst, Rhodamine 6G,
Scheme 51. Chemoselective synthesis of diaryldisulfides.
Figure 24. Mechanism for the formation diaryldisulfides from
aryldiazonium salts.
Adv. Synth. Catal. 2021, 363, 1782 – 1809
through a multicomponent reaction (MCR).[81] The
scope of diazonium salts containing both electron
donating and electron withdrawing groups were ex-
plored under the optimized conditions to afford the
desired aryl-S-thiosulfonate in moderate yields. meta-
and para-substituted aryldiazonium salts proceed
smoothly under the reaction conditions, while ortho
substituents on the diazonium salt furnished only a
trace amount of products. Similarly, diazonium salts
containing sterically hindered substituents under the
optimized reaction conditions afforded the desired
products in good yields (Scheme 52). At first, aryldia-
zonium salts react with thiourea to form an aryl
thiourea intermediate, which then generates thiopheno-
late anion, SO2 and urea from sodium metabisulfite.
Aryl radicals generated from the photocatalytic cycle
via SET captures SO2 to afford aryl sulfonyl radical,
which then couples with aryl sulfur radical (produced
from thiophenolate anion via SET) to form the desired
S-thiosulfonate product.[82]
8. Miscellaneous Reaction
8.1. Mechano-Chemicalborylation of Aryldiazo-
nium Salts
Yan and co-workers explored visible-light induced
borylation of aryldiazonium salts in 2012 under metal
free conditions.[83] Similarly, in 2017, Jose G. Hernan-
dez demonstrated the synthesis of aryl boronates by
milling aryl diazonium salt, bis(pinacolato)diboron
(B2pin2), and eosin Y with 25 mL PMMA milling jar
using 15 ZrO2 balls of 5 mm in diameter at 25 Hz to
afford moderate to good yields of the target material
(Scheme 53).[84] Aryldiazonium salts bearing functional
groups such as NO2 and I produced the correspond-
ing arylboronates despite in lower yields than other
functional groups.
8.2. Hydroxycarbonylation from Diazonium Salts
In 2015, Jacobi von Wangelin and Xiao independently
reported the first alkoxy carbonylation reaction cata-
lyzed by eosin-Y and fluorescein from aryldiazonium
Scheme 52. Synthesis of S-aryl thiosulfonate from coupling of
arenediazonium salt.
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Scheme 53. Synthesis of aryl boronic acid esters.
salts.[85] A few months later, Gu’s group demonstrated
the synthesis of diaryl ketones from aryldiazonium
salts using eosin Y as photocatalyst.[86] Interestingly,
Cyrille Gosset and co-workers described hydroxy
carbonylation of aryldiazonium salts with carbon
monoxide and Ru(bpy)3Cl2 as photocatalyst under
visible light irradiation (Scheme 54).[87] Aryl diazo-
nium salts containing a variety of electron-rich and
electron-poor substituents were studied, and in all the
cases, good yields of the final products were obtained.
Similarly, aryldiazonium salts generated in situ from
aniline under the standard conditions (1 mol % of
Ru(bpy)3Cl2, 20 equiv. of water, 10 bar of CO, and
blue LED irradiation) furnished the desired carboxylic
acid product. The aryl radicals generated react with the
CO leading to a benzoyl radical, which further oxidizes
Scheme 54. Synthesis of aryl carboxylic acid.
Scheme 55. Synthesis of aryl trifluoromethoxylated derivatives.
Adv. Synth. Catal. 2021, 363, 1782 – 1809
to form acylium cation. The acylium cation then reacts
with water to give the desired aryl carboxylic acid.
8.3. Copper Promoted Trifluoromethoxylation of
Aryldiazonium Salts
In 2015, Shaoqiang Yang et al. converted aryl diazo-
nium salts to aryl trifluoromethoxylated products using
dual copper-photoredox catalysis under mild condi-
tions (Scheme 55).[88] They investigated the scope of
various aryldiazonium salts containing electron with-
drawing, and electron donating substituents. In all
cases, the resultant products were obtained in good
yields except for ortho-substituted diazonium salts,
which afforded the desired product in very low yields
under the reaction conditions. In all the cases, simple
fluorinated by-products were observed in less than 6%
yield. Furthermore, the method’s synthetic utility was
shown using sulfamethoxazole and estrone derivatives
as the substrate, and the resultant products were
obtained in good yields. On the other hand, heteroaryl
diazonium salts under the reaction conditions afforded
no desired products. The mechanism involves the
reaction of Cu(I)OTf with TFMS (trifluoromethyl aryl
sulfonate) in the presence of CsF to produce anionic
Cu(I) trifluoromethoxide (in situ), which on oxidation
by Ru3 + via SET results in a Cu(II) intermediate. The
Cu(II) species then reacts with aryl radicals generated
from the photocatalytic cycle to form an aryl Cu-
(III) OCF3 adduct; this high-valent Cu(III) species
finally undergoes reductive elimination to give the
desired product, as shown in Figure 25.
8.4. Difluoromethylthiolation of Aryldiazonium
Salts
Synthesis of difluoromethyl thioethers from aryldiazo-
nium salts were described by Shen et al. using a silver
complex [(SIPr)Ag(SCF2H)].[89] Similarly, Wengui
Figure 25. Proposed mechanism for the synthesis of aryl
trifluoromethoxylated products.
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Wang et al. explored photoredox-mediated
difluoromethyl thioether synthesis from aryldiazonium
salts using an inexpensive reagent, PhSO2SCF2H
(Shen’s reagent).[90] The reaction was carried out using
5 mol% of Ru(bpy)3(PF6)2 as the photocatalyst,
2 equiv. of sodium ascorbate as additive, and CH3CN
as the solvent. Aryldiazonium salts containing various
functional groups furnished the desired products in
moderate to good yields except for substrates contain-
ing electron withdrawing groups, which afforded low
yields. Hetero-aryldiazonium salts under the standard
conditions afforded only moderate yields. Similarly,
disubstituted and trisubstituted diazonium salts fur-
nished the desired difluoromethyl thioethers in 22–
67% yields (Scheme 56).
8.5. Organogold (III) Complexes from Aryldiazo-
nium Salts
In 2016, Long Huang and co-workers developed a
method for synthesizing aryl-gold (III) complexes
from gold (I) complexes of both phosphine and
Scheme 56. Synthesis of difluoromethylthioethers.
Scheme 57. Synthesis of aryl-gold complexes.
Adv. Synth. Catal. 2021, 363, 1782 – 1809
carbene ligands with aryldiazonium salts. With P, N-
chelating ligands, cationic six or five-membered aryl-
gold (III) complexes were isolated in the form of salts
with weakly coordinating counter anion (tetrafluorobo-
rate or triflate). They succeeded in achieving not only
the cationic complexes but also neutral aryl-gold (III)
dichloro complexes from gold (I) complexes of
monodentate P-ligands or N-heterocyclic carbene
ligands and aryldiazonium chlorides (which was
synthesized in situ from the corresponding aniline and
treated with gold (I) complexes) under irradiation of
visible light (Scheme 57).[91]
8.6. Synthesis of Trifluoromethylselenolated Arenes
In 2018, Clement Ghiazza et al. achieved the synthesis
of trifluoromethyl selenolated arenes from diazonium
salts and trifluoromethyltoluene-selenosulfonate
(TsSeCF3) in the presence of organic photocatalyst
(eosin Y) under irradiation of white LEDs in good
yields (Scheme 58).[92] Aryl diazonium salts bearing
both electron donor and acceptor substituents success-
fully afforded trifluoromethyl selenolated arenes in
good to excellent yields. Similarly, sterically hindered
substituents also gave good yields. Notably, ortho
substituents on the diazonium salts gave the desired
products in low yields. Further, they extended this
methodology to higher homologs of TsSeCF3, such as
TsSeCF2CF3 and TsSeCF2CF2CF3, and obtained the
desired products in good yields under the standard
conditions.
9. Conclusion
In this review, we have provided an overview of the
recent advances in visible-light mediated organic trans-
formations using aryldiazonium salts as the aryl radical
precursor. Beginning from Stanford’s report on ligand-
directed C H arylation, a huge surge in the use of aryl
diazonium salts in photoredox arylation has been
Scheme 58. Synthesis of trifluoromethylselenolated arenes.
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observed. Aryldiazonium salts show a variety of
reactivity, such as the addition to alkenes/alkynes,
cross-coupling, oxidative addition and other miscella-
neous reactions with different transition metal photo-
catalysts such Ru, Ir, etc. and organic dyes such as
Eosin Y, 9,10-dihydroacridine, etc. and with various
light source. [10]
Dual photoredox catalysis is a very promising area
for the activation of many unreactive C H bonds and [11]
for the synthesis of some important molecular scaf-
folds. In this direction, gold and palladium show some [12]
interesting reactivity patterns, and more study in this
direction is warranted. Another less explored reaction [13]
is the use of aryl diazonium salts for the synthesis of
[14]
azo compounds and other C N bond forming reactions
under photoredox conditions. Similarly, heterogeneous
photocatalysts such as PANI-g-C3N4 TiO2 is another
[15]
exciting avenue for carrying out the arylation reactions
in a cost-effective way by reusing the photocatalyst. [16]
Acknowledgements [17]
P.G. thanks DST-SERB for a Ramanujan fellowship (SB/S2/
RJN-041/2017). S.S.B & P.M thanks IISER Tirupati for financial [18]
support& P.Y thanks CSIR, India for a JRF fellowship.
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