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org/journal/ascecg Perspective

Prospects and Challenges in Organosulfur Chemistry

Ming Wang and Xuefeng Jiang*

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ABSTRACT: Sulfur-containing molecules are increasingly crucial in chemistry-related fields

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and are widely applied in life science, material science, food science, and pharmaceutical
science. This perspective focuses on the introduction of green sulfurizing reagents and
sustainable sulfurizing methodologies to realize diverse kinds of functionalized transformations
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and synthetic applications. The text is organized according to the structure of the sulfur-
containing molecules and the corresponding synthetic method. It is expected to be of interest
to organic chemistry professionals who wish to better understand the insights and applications
of organosulfur chemistry transformations.

KEYWORDS: Sulfur, Sulfide, Polysulfides, Sulfone, Sulfoxides, Sulfur dioxide, Pharmaceutical, Material

■ INTRODUCTION
The sulfur element, which can adopt diverse oxidation states,
standpoint of green and sustainable strategies for sulfide
construction. Moreover, recent synthetic methods aimed at
has extensive applications in pharmaceuticals, agrochemicals, overcoming the challenges in sulfur chemistry are also
organic materials, and life phenomena (Figures 1 and 2).1−4 A introduced.
remarkable range of simple organosulfur compounds are Green Construction of Sulfides (Strong Coordination
known to be widely distributed throughout allium plants and and Foul Smell). Thiols and thiophenols are the most widely
are commonly the key factor in the odor and flavor of daily used original materials in the preparation of sulfur-containing
comestibles.5,6 The diversified oxidation states enable sulfides molecules. However, most of these chemicals have an
to acquire significant functions for pharmacokinetics and unpleasant smell. Moreover, the strong coordination from
thiols and thiophenols to metal catalysts leads to deactivation
pharmacodynamics in the development of pharmaceuticals.
of the catalyst because of the lone pair of electrons on sulfur.
Several representative sulfur-containing drugs in distinct
The strong coordination with metal catalysts and unpleasant
oxidation states are shown in Figure 1. The unique optical
odor of thiols are the primary challenges in sulfur chemistry.
and electronic properties of sulfur also make this element
To solve these problems, green sulfurizing reagents and
indispensable in organic photoconducting materials and
methods are constantly being pursued. In recent years, masked
batteries. Representative sulfur-containing materials are
sulfurizing reagents and corresponding sulfurizing strategies
depicted in Figure 2.7−9 Despite the multiple valuable
have been developed for the synthesis of various types of
properties of sulfur, variations in the abundance of sulfur
sulfides (Scheme 1). Masking groups regulate the electronic,
lead to synthetic challenges. First, because of the lone pair of
steric, and resonance effects, enabling sulfurizing reagents to
electrons on the sulfur atoms, coordination of thiols to metal
have much better performance than traditional thiol chemistry.
catalysts generally poisons the catalysts, and these chemicals
Due to the masking effect, the introduction of sulfur via
are accompanied by unpleasant odors. Second, a disulfide is a
inorganic sulfur salts is odorless and prevents the coordination
unique motif that can undergo reversible cleavage and
of sulfur atoms to metal catalysts. For example, S-alkyl/aryl
formation, and when there is only a slight difference in
bonds, selective cleavage between the S−S bond and S−C/S−
X bonds can occur. Third, the multiple levels of hypervalent Received: November 10, 2021
sulfide lead to challenges in oxidation selectivity and Revised: December 14, 2021
compatibility. The increasingly extensive application of sulfides Published: January 3, 2022
requires innovative sulfurizing reagents and corresponding
synthetic transformations. This perspective aims to provide an
overview of the challenges in sulfur chemistry from the

© 2022 American Chemical Society https://doi.org/10.1021/acssuschemeng.1c07636

671 ACS Sustainable Chem. Eng. 2022, 10, 671−677
ACS Sustainable Chemistry & Engineering
Figure 1. Sulfur-containing pharmaceuticals.
thiosulfate salt, discovered by Bunte, is an excellent candidate
for sulfur introduction, especially in transition-metal-catalyzed
systems, as discussed by Wang et al.10 The sulfur trioxide on a
sulfur atom effectively serves as an electron-withdrawing,
sterically bulky, and conjugated group to eliminate odor and
prevent poisoning.10
Elemental sulfur, as an abundantly available, inexpensive,
odorless, and easy to handle chemical feedstock, is the
byproduct of the petroleum desulfurization process. In
addition, elemental sulfur is the richest in sulfur content and
displays high atomic economy to employ as a sulfur source.
Therefore, elemental sulfur will be one of the most ideal
sustainable raw materials for the synthesis of sulfur-containing
compounds. In the developed sulfide construction reactions
672
pubs.acs.org/journal/ascecg Perspective
involving elemental sulfur, it can play various roles such as a
sulfur source, oxidant, and reductant.11−13
Synthesis of Unsymmetrical Polysulfides (with Accu-
rate Control of Sulfur Number Dimension). Avoiding the
generation of symmetrical disulfides in the synthesis of
unsymmetrical disulfides has always been a challenge. Another
obstacle in the synthesis of polysulfides is avoiding the cleavage
of weak S−S bonds. S−S bonds, with a low bond dissociation
energy (48−66 kcal/mol), are inclined to dissociate during
their transformation. Masked polysulfurizing reagents are
needed to avoid the use of unstable RSSH. The cleavage rate
of the C−S bond can be determined through kinetic control
and the electron-withdrawing effect of the masking group,
simultaneously increasing the thermodynamic stability of the
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Figure 2. Sulfur-containing materials.

Scheme 1. Masked Sulfurizing Strategy

S−S bond by restraining strong coordination from sulfur to the Scheme 2. Construction of Unsymmetrical Polysulfides
transition metal. In addition, the pH value of the system plays a
key role in achieving highly selective cleavage of the C−S bond
instead of the S−S bond in the synthesis of polysulfide systems.
Oxidative cross-coupling between two different thiols, in which
symmetric disulfide byproducts are unavoidable, is a traditional
pathway. In recent years, several efficient protocols have been
reported for the synthesis of unsymmetrical disulfides (Scheme
2). For example, the exchange method between two distinct
symmetrical disulfides was disclosed for the construction of
unsymmetrical disulfides.14 Various cross-coupling reactions
for unsymmetrical disulfide synthesis have been explored by
employing thiosulfate salt (Bunte salt) and acetyl-, methoxyl-,
and phthalimide-masked disulfurizing reagents.15−20
Recently, radical substitution on tetrasulfides was demon-
strated to be an effective means for unsymmetric disulfide
synthesis. In this process, alkyl and aryl radicals, generated
thermally or photochemically, underwent substitution on
readily accessible dialkyl, diaryl, and diacyl tetrasulfides to
yield the corresponding disulfides.21 Although these works
have achieved retention of fragile S−S bonds, the present
method is still unsuitable for unsymmetrical tetrasulfide and
cyclic polysulfide. Molecular hybridization, in which a
polysulfide-containing hybrid linkage is an outstanding
reversible linker, is a cutting-edge technology in the develop- polysulfides in antibody−drug conjugates (ADCs), small-
ment of modern drugs. The direct late-stage construction of molecule drug conjugates (SMDCs), peptide drug conjugates
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ACS Sustainable Chemistry & Engineering
(PDCs), THIOMAB antibody−drug conjugates (TDCs), and
other drug conjugates is a promising technique for the future
development of highly compatible polysulfurizing systems.
Hydrogen polysulfide (H2Sn, n > 1), as a key type of small
signaling molecule in reactive sulfur species, has attracted
increasing attention. H2Sn and hydrogen sulfide (H2S) form a
redox pair, transforming and coexisting in biological systems.
Recent studies have shown that H2Sn may be the real
transducer in physiological processes, while H2S is the final
product of H2Sn, such as in the cardiovascular system, ion
channels, oxidative posttranslational modification, antioxida-
tion, and cytoprotection.22−24
Controllability of Hypervalent Sulfur Construction
(Accurate Control of the Sulfur Oxidation State
Dimension). For the construction of hypervalent sulfur, the
control of different oxidative states, such as sulfoxide and
sulfone, is a challenge. On the other hand, the heteroatom-
containing and chirality-containing backbones that are wide-
spread in hypervalent sulfur-containing drug molecules are
always sensitive and incompatible with strong oxidative
conditions. Therefore, the use of mild conditions for the
construction of hypervalent sulfur is imperative. The utilization
of green photocatalytic or electrocatalytic conditions with air
or water as the green oxygen source is an ideal strategy.25,26
For example, a straightforward, green, and broadly applicable
electrochemical continuous-flow procedure to oxidize thio-
ethers and thiols has been developed.22 Water is used as the
source of oxygen to enable oxidation. A wide variety of
functionalized sulfoxides and sulfones can be accessed via
alteration of the applied voltage (Scheme 3).
Scheme 3. Controllable Sulfonation and Sulfoxidation
Chiral sulfoxides are considered ideal ligand candidates for
transition-metal-catalyzed asymmetric reactions due to their
stability and special S-stereogenic control.27−33 For example,
sulfoxide−nitrogen, sulfoxide−oxygen, sulfoxide−sulfur, sulf-
oxide−phosphine, and sulfoxide−olefin ligands have been well
developed for use in, for example, asymmetric allylic alkylation,
Diels−Alder reactions, and hydrogenation (Figure 3).
However, the scope of reactions explored with these ligands
remains relatively limited. Extending the utility of sulfoxide
ligands to more transition-metal-catalyzed reactions, including
frontier research areas, is expected to be a topic of interest in
the future. For example, although many other types of chiral
ligands have been employed in a radical process to realize
asymmetric catalysis, no chiral sulfoxide ligand has yet been
applied in asymmetric catalysis related to a radical process.
Therefore, the design and synthesis of new chiral sulfoxide
ligands for the development of new sulfoxide ligand-catalyzed
reactions are still in high demand and a challenging issue for
the future.
Sulfur ylides, which are composed of a carbanion and a
positively charged sulfur atom, are another kind of hypervalent
sulfur motif. They form a family of versatile reagents that have
been widely used as one-carbon synthons in many classic
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Figure 3. Chiral sulfoxides ligands.
transformations (Scheme 4).34 For example, epoxidations and
aziridinations of sulfur ylides are important strategies for the
Scheme 4. Application of Sulfur Ylides
synthesis of oxirane and aziridine derivatives.35 Cyclopropana-
tion of α,β-unsaturated aldehydes with sulfur ylides has been
well developed.36 Sulfur ylides are powerful materials for the
construction of functionalized heterocycles via cycloaddition
reactions.37−40 The rearrangement of sulfur ylides offers a
unique approach for the construction of S-substituted
quaternary centers.41,42 However, sulfur ylides traditionally
react as nucleophiles in these transformations, which restricts
their application as single-carbon synthons to only a handful of
valuable reactions. Therefore, a considerable breadth of
reactivity can be accessed via the introduction of transition
metal catalysis. The combination of transition metal catalysts
with sulfur ylides is an unexploited area of organic synthesis,
where further exciting developments can be anticipated in the
future.
Parallel-Oxidative-State Introduction of Sulfur Diox-
ide. Sulfone construction by introducing sulfur dioxide into
organic frameworks is an important strategy to overcome the
compatibility problems. Willis et al.43 and Ye and Wu44
explored the insertion of the SO2 motif in a three-component
coupling reaction by using DABSO [DABCO·(SO2)2] as a
sulfur dioxide surrogate, which was prepared by Santos and
Mello in 1988.45 Subsequently, several inorganic salts, such as
sodium metabisulfite,46,47 sodium dithionite,48,49 and thiourea
dioxide, 50,51 served as sulfur dioxide sources for the
construction of sulfones. In these strategies, the SO2 motif in
inorganic sulfur salts possesses a sufficiently active hybridized
SOMO to participate in a radical process. The constructions of
aryl−aryl sulfone, aryl−alkyl sulfone, alkyl−alkyl sulfone,
tertiary sulfones, methyl sulfone, and sulfamide with high
compatibility were comprehensively achieved via the parallel-
oxidative-state introduction of a hypervalent sulfur moiety.
Since there is no strong oxidant to increase the oxidation state
of sulfur, sensitive groups, such as amino, hydroxyl, sulfide, and
pyridinyl groups, are compatible in these systems. Although the
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strategy of introducing parallel-oxidative states of hypervalent https://pubs.acs.org/10.1021/acssuschemeng.1c07636

sulfur has been widely used for hypervalent sulfur construction,
the synthesis of chiral hypervalent sulfur and the compatibility Notes
with more sensitive groups via this strategy are still unsolved. The authors declare no competing financial interest.

■ SUMMARY AND PROSPECTIVES

This perspective describes cutting-edge advances to resolve the
Biographies

traditional challenges in organosulfur chemistry, which include

the development of green and sustainable sulfur chemistry.
The exploitation of lower toxicity, safer, odorless, stable, high
atom economy, and inexpensive sulfurizing reagents and
sustainable sulfurizing methodologies to realize diverse kinds
of functionalized transformations will make sulfur chemistry
green and sustainable. Diverse sulfide constructions are in great
demand not only in chemistry but also in chemistry-related
fields because sulfur-containing motifs enable a wide range of
applications. Although there have been excellent breakthroughs
in organosulfur research in recent years, various desires related
to sulfides are rapidly emerging, especially in polysulfation with
biocompatible conditions and hypervalent sulfur synthesis in
an eco-friendly manner. For biology, the formation and Ming Wang received his Ph.D. degree in 2011 from East China
cleavage of polysulfides will help elucidate the critical roles
University of Science and Technology. From 2011 to 2014, he was a
of sulfur in proteins and access pathways, leading to significant
impacts on biological systems and helping us to understand postdoctoral researcher under the guidance of Professor Yonggui
relationships among biological phenomena. For drug discov- Robin Chi at Nanyang Technological University, Singapore. In 2014,
ery, diverse sulfides and hypervalent sulfur compounds are he joined East China Normal University and is currently an associate
necessary to pertinently adjust drug metabolisms and control professor.
the solubility balance, and they are also potential reversible
linkers for biomacromolecule drug conjugates. For organic
materials, novel types of conjugated and high-sulfur-content
polymers or monomers will result in high resonance energy
and polarizability, leading to promising charge transport
properties. Explanations of biological pathways, modern drug
discovery, and excellent photoelectric materials are encourag-
ing the rapid development of organosulfur, and conversely,
sulfur chemistry is supplying continuous new advances in core
domains and emerging fields. How to activate these stable,
odorless, and cheap sulfur reagents, such as elemental sulfur,
sodium thiosulfate, sodium metabisulfite, and sodium
dithionite, as sulfur sources in a mild condition for the
construction of biological, pharmaceutical, and material sulfur-
containing molecules will be a long-term challenge in
sustainable sulfur chemistry. With constant discoveries of Xuefeng Jiang is a professor at East China Normal University. He
vulcanization rules, organosulfur industry applications will received his B.S. degree in 2003 from Northwest University, China.
enter a new era with the philosophy of sustainable materials He then joined Professor Shengming Ma’s research group at the
and energy cycle.

■
AUTHOR INFORMATION
Corresponding Author
Xuefeng Jiang − Shanghai Key Laboratory of Green Chemistry
and Chemical Process, School of Chemistry and Molecular
Engineering,, East China Normal University, Shanghai
200062, P. R. China; State Key Laboratory of Elemento-
Organic Chemistry, Nankai University, Tianjin 300071, P. R.
China; orcid.org/0000-0002-1849-6572;
Email: xfjiang@chem.ecnu.edu.cn
Author
Ming Wang − Shanghai Key Laboratory of Green Chemistry
and Chemical Process, School of Chemistry and Molecular
Engineering,, East China Normal University, Shanghai
200062, P. R. China; orcid.org/0000-0003-0388-4473
Complete contact information is available at:
675
Shanghai Institute of Organic Chemistry, Chinese Academy of
Sciences, where he received his Ph.D. degree in 2008. From 2008 to
2011, he worked as a postdoctoral researcher on the total synthesis of
natural products in the research group of Professor K. C. Nicolaou at
The Scripps Research Institute. His independent research interests
have focused on green sulfur chemistry and methodology-oriented
total synthesis.
■ ACKNOWLEDGMENTS
The authors are grateful for the financial support provided by
NSFC (22125103, 22071057, and 21871089), STCSM
(20XD1421500 and 20JC1416800), Innovative Research
Team of High-Level Local Universities in Shanghai (SSMU-
ZLCX20180501), Professor of Special Appointment (Eastern
Scholar) at Shanghai Institutions of Higher Learning, and the
Fundamental Research Funds for the Central Universities.
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ACS Sustainable Chemistry & Engineering
■
REFERENCES
(1) Ilardi, E. A.; Vitaku, E.; Njardarson, J. T. Data-mining for sulfur
and fluorine: An evaluation of pharmaceuticals to reveal opportunities
for drug design and discovery. J. Med. Chem. 2014, 57, 2832−2842.
(2) Devendar, P.; Yang, G.-F. Sulfur-containing agrochemicals. Top.
Curr. Chem. 2017, 375, 82.
(3) Cinar, M. E.; Ozturk, T. Thienothiophenes, dithienothiophenes,
and thienoacenes: syntheses, oligomers, polymers, and properties.
Chem. Rev. 2015, 115, 3036−3140.
(4) Wang, N.; Saidhareddy, P.; Jiang, X. Construction of sulfur-
containing moieties in the total synthesis of natural products. Nat.
Prod. Rep. 2020, 37, 246−275.
(5) Block, E. Flavor artifacts. J. Agric. Food Chem. 1993, 41, 692−
692.
(6) Block, E.; Bayer, T. (Z,Z)-d,l-2,3-Dimethyl-1,4-butanedithial
S,S’-dioxide: a novel biologically active organosulfur compound from
onion. Formation of vic-disulfoxides in onion extracts. J. Am. Chem.
Soc. 1990, 112, 4584−4585.
(7) Worthington, M. J. H.; Kucera, R. L.; Chalker, J. M. Green
Chemistry and Polymers Made from Sulfur. Green Chem. 2017, 19,
2748−2761.
(8) Zhang, Y.; Glass, R. S.; Char, K.; Pyun, J. Recent Advances in the
Polymerization of Elemental Sulphur, Inverse Vulcanization and
Methods to Obtain Functional Chalcogenide Hybrid Inorganic/
Organic Polymers (CHIPs). Polym. Chem. 2019, 10, 4078−4105.
(9) Chalker, J. M.; Worthington, M. J. H.; Lundquist, N. A.; Esdaile,
L. J. Synthesis and Applications of Polymers Made by Inverse
Vulcanization. Top. Curr. Chem. 2019, 377, 14.
(10) Wang, M.; Li, Y.; Jiang, X. Recent advances in sulfuration
chemistry enabled by Bunte salts. Aldrich. Acta 2020, 53, 19−35.
(11) Nguyen, T. B. Elemental Sulfur and Molecular Iodine as
Efficient Tools for Carbon-Nitrogen Bond Formation through Redox
Reactions. Asian J. Org. Chem. 2017, 6, 477−491.
(12) Nguyen, T. B. Recent Advances in Organic Reactions Involving
Elemental Sulfur. Adv. Synth. Catal. 2017, 359, 1066−1130.
(13) Nguyen, T. B. Recent Advances in the Synthesis of
Heterocycles via Reactions Involving Elemental Sulfur. Adv. Synth.
Catal. 2020, 362, 3448−3484.
(14) Arisawa, M.; Yamaguchi, M. Rhodium-Catalyzed Disulfide
Exchange Reaction. J. Am. Chem. Soc. 2003, 125, 6624−6625.
(15) Alonso, M. E.; Aragona, H. Sulfide Synthesis in Preparation of
Unsymmetrical Dialkyl disulfides: sec-Butyl Isopropyl Disulfide. Org.
Synth. 1978, 58, 147.
(16) Xiao, X.; Feng, M.; Jiang, X. New design of a disulfurating
reagent: Facile and straightforward pathway to unsymmetrical
disulfanes by copper-catalyzed oxidative cross-coupling. Angew.
Chem., Int. Ed. 2016, 55, 14121−14125.
(17) Xiao, X.; Xue, J.; Jiang, X. Polysulfurating reagent design for
unsymmetrical polysulfide construction. Nat. Commun. 2018, 9, 2191.
(18) Xue, J.; Jiang, X. Unsymmetrical Polysulfidation via Designed
Bilateral Disulfurating Reagents. Nat. Commun. 2020, 11, 4170.
(19) Gao, W.; Tian, J.; Shang, Y.; Jiang, X. Steric and stereoscopic
disulfide construction for cross-linkage via N-dithiophthalimides.
Chem. Sci. 2020, 11, 3903−3908.
(20) Xue, J.; Jiang, X. Polysulfuration via a Bilateral Thiamine
Disulfurating Reagent. Org. Lett. 2020, 22, 8044−8048.
(21) Wu, Z.; Pratt, D. A. Radical substitution provides a unique
route to disulfides. J. Am. Chem. Soc. 2020, 142, 10284−10290.
(22) Lu, M.; Liu, Y.-H.; Goh, H. S.; Wang, J. J. X.; Yong, Q.-C.;
Wang, R.; Bian, J.-S. Hydrogen sulfide inhibits plasma renin activity. J.
Am. Soc. Nephrol. 2010, 21, 993−1002.
(23) Salloum, F. N. Hydrogen sulfide and cardioprotection-
mechanistic insights and clinical translatability. Pharmacol. Ther.
2015, 152, 11−17.
(24) Wallace, J. L.; Wang, R. Hydrogen sulfide-based therapeutics:
exploiting a unique but ubiquitous gasotransmitter. Nat. Rev. Drug
Discovery 2015, 14, 329−345.
(25) Laudadio, G.; Straathof, N. J. W.; Lanting, M. D.; Knoops, B.;
Hessel, V.; Noël, T. An environmentally benign and selective
676
pubs.acs.org/journal/ascecg Perspective
electrochemical oxidation of sulfides and thiols in a continuous-flow
microreactor. Green Chem. 2017, 19, 4061−4066.
(26) Li, Y.; Rizvi, S. A.; Hu, D.; Sun, D.; Gao, A.; Zhou, Y.; Li, J.;
Jiang, X. Selective Late-Stage Oxygenation with Ground-State Oxygen
Based on Sulfides by Uranyl Photocatalysis. Angew. Chem., Int. Ed.
2019, 58, 13499−13506.
(27) Thaler, T.; Guo, L.-N.; Steib, A. K.; Raducan, M.; Karaghiosoff,
K.; Mayer, P.; Knochel, P. Sulfoxide-Alkene Hybrids: A New Class of
Chiral Ligands for the Hayashi-Miyaura Reaction. Org. Lett. 2011, 13,
3182−3185.
(28) Zhang, Z.-M.; Chen, P.; Li, W.; Niu, Y.; Zhao, X.-L.; Zhang, J.
A New Type of Chiral Sulfinamide Monophosphine Ligands:
Stereodivergent Synthesis and Application in Enantioselective Gold-
(I)-Catalyzed Cycloaddition Reactions. Angew. Chem., Int. Ed. 2014,
53, 4350−4354.
(29) Li, Y.; Xu, M.-H. Simple sulfur-olefins as new promising chiral
ligands for asymmetric catalysis. Chem. Commun. 2014, 50, 3771−
3782.
(30) Chen, J.; Chen, J.; Lang, F.; Zhang, X.; Cun, L.; Zhu, J.; Deng,
J.; Liao, J. A C2-Symmetric Chiral Bis-Sulfoxide Ligand in a Rhodium-
Catalyzed Reaction: Asymmetric 1,4-Addition of Sodium Tetraar-
ylborates to Chromenones. J. Am. Chem. Soc. 2010, 132, 4552−4553.
(31) Robak, M. T.; Herbage, M. A.; Ellman, J. A. Synthesis and
Applications of tert-Butanesulfinamide. Chem. Rev. 2010, 110, 3600−
3740.
(32) Liu, M.; Shen, A.; Sun, X.-W.; Deng, F.; Xu, M.-H.; Lin, G.-Q.
Dramatic lithium chloride effect on the reaction stereocontrol in Zn-
mediated asymmetric cinnamylation: highly practical synthesis of β-
aryl homoallylic amines. Chem. Commun. 2010, 46, 8460−8462.
(33) Ferreira, F.; Botuha, C.; Chemla, F.; Pérez-Luna, A. tert-
Butanesulfinimines: structure, synthesis and synthetic applications.
Chem. Soc. Rev. 2009, 38, 1162−1186.
(34) Kaiser, D.; Klose, I.; Oost, R.; Neuhaus, J.; Maulide, N. Bond-
Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium
Salts, Sulfur Ylides, and Sulfinate Salts. Chem. Rev. 2019, 119, 8701−
8780.
(35) Illa, O.; Namutebi, M.; Saha, C.; Ostovar, M.; Chen, C. C.;
Haddow, M. F.; Nocquet-Thibault, S.; Lusi, M.; McGarrigle, E. M.;
Aggarwal, V. K. Practical and Highly Selective Sulfur Ylide-Mediated
Asymmetric Epoxidations and Aziridinations Using a Cheap and
Readily Available Chiral Sulfide: Extensive Studies To Map Out
Scope, Limitations, and Rationalization of Diastereo- and Enantiose-
lectivities. J. Am. Chem. Soc. 2013, 135, 11951−11966.
(36) Kunz, R. K.; MacMillan, D. W. Enantioselective Organo-
catalytic Cyclopropanations. The Identification of a New Class of
Iminium Catalyst Based upon Directed Electrostatic Activation. J. Am.
Chem. Soc. 2005, 127, 3240−3241.
(37) Chen, J.-R.; Dong, W.-R.; Candy, M.; Pan, F.-F.; Jörres, M.;
Bolm, C. Enantioselective Synthesis of Dihydropyrazoles by Formal
[4 + 1] Cycloaddition of in Situ-Derived Azoalkenes and Sulfur
Ylides. J. Am. Chem. Soc. 2012, 134, 6924−6927.
(38) Huang, X.; Peng, B.; Luparia, M.; Gomes, L. F. R.; Veiros, L. F.;
Maulide, N. Gold-Catalyzed Synthesis of Furans and Furanones from
Sulfur Ylides. Angew. Chem., Int. Ed. 2012, 51, 8886−8890.
(39) Kramer, S.; Skrydstrup, T. Gold-Catalyzed Carbene Transfer to
Alkynes: Access to 2,4-Disubstituted Furans. Angew. Chem., Int. Ed.
2012, 51, 4681−4684.
(40) Huang, X.; Goddard, R.; Maulide, N. A Direct Ylide Transfer to
Carbonyl Derivatives and Heteroaromatic Compounds. Angew. Chem.,
Int. Ed. 2010, 49, 8979−8983.
(41) Zhang, Z.; Sheng, Z.; Yu, W.; Wu, G.; Zhang, R.; Chu, W.-D.
M.; Zhang, Y.; Wang, J. Catalytic Asymmetric Trifluoromethylth-
iolation via Enantioselective [2,3]-Sigmatropic Rearrangement of
Sulfonium Ylides. Nat. Chem. 2017, 9, 970−976.
(42) Lin, X.; Tang, Y.; Yang, W.; Tan, F.; Lin, L.; Liu, X.; Feng, X.
Chiral Nickel(II) Complex Catalyzed Enantioselective Doyle-Kirmse
Reaction of α-Diazo Pyrazoleamides. J. Am. Chem. Soc. 2018, 140,
3299−3305.
https://doi.org/10.1021/acssuschemeng.1c07636
ACS Sustainable Chem. Eng. 2022, 10, 671−677
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Perspective

(43) Nguyen, B.; Emmett, E. J.; Willis, M. C. Palladium-catalyzed

aminosulfonylation of aryl halides. J. Am. Chem. Soc. 2010, 132,
16372−16373.
(44) Ye, S.; Wu, J. A palladium-catalyzed three-component coupling
of arylboronic acids, sulfur dioxide and hydrazines. Chem. Commun.
2012, 48, 7753−7755.
(45) Santos, P. S.; Mello, M. T. S. The Raman Spectra of Some
Molecular Complexes of 1-Azabicyclo[2.2.2]octane and 1,4-
Diazabicyclo[2.2.2]octane. J. Mol. Struct. 1988, 178, 121−133.
(46) Meng, Y.; Wang, M.; Jiang, X. Multicomponent Reductive
Cross-Coupling of an Inorganic Sulfur Dioxide Surrogate: Straightfor-
ward Construction of Diversely Functionalized Sulfones. Angew.
Chem., Int. Ed. 2020, 59, 1346−1353.
(47) Meng, Y.; Wang, M.; Jiang, X. Transition-Metal-Free Reductive
Cross-Coupling Employing Metabisulfite as a Connector: General
Construction of Alkyl-Alkyl Sulfones. CCS Chem. 2021, 3, 17−24.
(48) Li, Y.; Chen, S.; Wang, M.; Jiang, X. Sodium Dithionite-
Mediated Decarboxylative Sulfonylation: Facile Access to Tertiary
Sulfones. Angew. Chem., Int. Ed. 2020, 59, 8907−8911.
(49) Li, Y.; Liu, T.; Qiu, G.; Wu, J. Catalyst-Free Sulfonylation of
(Hetero)aryl Iodides with Sodium Dithionite. Adv. Synth. Catal. 2019,
361, 1154−1159.
(50) Ye, S.; Li, Y.; Wu, J.; Li, Z. Thiourea dioxide as a source of
sulfonyl groups: photoredox generation of sulfones and sulfonamides
from heteroaryl/aryl halides. Chem. Commun. 2019, 55, 2489−2492.
(51) Li, K.; Wang, M.; Jiang, X. Full-Spectrum Fluoromethyl
Sulfonation via Modularized Multicomponent Coupling. CCS Chem.
2021, 3, 1735−1743.

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