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Vinyl sulfones

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Alkenyl sulfones can be stereoselectively synthesized from alkenes or alkynes using sodium sulfinates in the presence of CuI-bpy as catalyst and oxygen. The reaction of alkenes gives (E)-alkenyl sulfones via anti addition of the sulfonyl cation followed by an elimination process. Furthermore, the employment of alkynes produces (E)-β-haloalkenyl sulfones in the presence of potassium halides.
N. Taniguchi, Synlett, 2011, 1308-1312.

A simple and efficient electrochemical sulfonylation of organoboronic acids with sodium arylsulfinate salts provides a variety of aryl, heteroaryl, and alkenylsulfones in good yields at room temperature under catalyst- and additive-free conditions.
W. Yao, K. Lv, Z. Xie, H. Qui, M. Ma, J. Org. Chem., 2023, 88, 2296-2305.

The use of inorganic sodium metabisulfite as the sulfur dioxide surrogate and di-tert-butyl peroxide as source of the methyl radical enables a direct C-H methylsulfonylation of alkenes. This method provides convenient access to (E)-2-methyl styrenyl sulfones in good yields.
F.-S. He, Y. Gong, P. Rojsitthisak, J. Wu, J. Org. Chem., 2019, 84, 13159-13163.

An iodine-catalyzed functionalization of various olefins and alkynes and direct decarboxylative functionalization of cinnamic and propiolic acids with TosMIC provides highy valuable vinyl, allyl, and β-iodo vinylsulfones. This simple, efficient, and environmentally benign approach is attractive to both synthetic and medicinal chemistry.
L. Kadari, R. K. Palakodety, L. P. Yallapragada, Org. Lett., 2017, 19, 2580-2583.

An electrochemical sulfonylation reaction of styrenes with sodium arylsulfinates as sulfonylating reagents, a catalytic amount of KI as a redox mediator, and Bu4NBF4 as the electrolyte provides vinyl sulfones in good yields. Substrates bearing either electron-donating or electron-withdrawing groups are tolerated.
P.-L. Wang, H. Gao, Z.-S. Jiang, C. Li, Z.-H. Tian, P.-H. Li, Synlett, 2020, 31, 1720-1724.

Copper-catalyzed hydrosulfonylations of both terminal and internal alkynes can be carried out using sodium sulfinates in air. The procedure affords syn-selectively (E)-alkenyl sulfones in good yields.
N. Taniguchi, Synlett, 2012, 23, 1245-1249.

An efficient hydrosulfonylation of alkynes using sodium arene sulfinates is catalyzed by Cu(OTf)2 under microwave irradiation.Various vinyl sulfones were obtained in very good yields and with high regio- and stereoselectivity. Short reaction times, simple reaction conditions and low catalyst loading are the remarkable features of this protocol.
G. M. Shelke, V. K. Rao, K. Pericherla, A. Kumar, Synlett, 2014, 25, 2345-2349.

The reaction of alkenes with sodium arene sulfinates in the presence of potassium iodide and sodium periodate and a catalytic amount of acetic acid provides vinyl sulfones at room temperature. The products are formed in high yields within hours.
B. Das, M. Lingaiah, K. Damodar, N. Bhunia, Synthesis, 2011, 2941-2644.

A facile I2O5-mediated direct oxidative coupling of aromatic alkenes with thiols provides various (E)-vinyl sulfones from readily available starting materials with excellent regioselectivity under metal-free conditions.
L. Wang, H. Yue, D. Yang, H. Cui, M. Zhu, J. Wang, W. Wei, H. Wang, J. Org. Chem., 2017, 82, 6857-6864.

An efficient and environmentally friendly phosphoric acid mediated decarboxylative coupling of sodium sulfinates with phenylpropiolic acids provides vinyl sulfones.
G. Rong, J. Mao, H. Yan, Y. Zheng, G. Zhang, J. Org. Chem., 2015, 80, 7652-7657.

Visible-light-induced decarboxylative sulfonylation of cinnamic acids with aryl sulfonate phenol esters offers a mild and green approach for the synthesis of vinyl sulfones with excellent functional group compatibility under photocatalyst and oxidant-free conditions.
Q.-Q. Ge, J.-S. Qian, J. Xuan, J. Org. Chem., 2019, 84, 8691-8701.

Reactions of cinnamic acids with aromatic sulfinic acid sodium salts in the presence of a catalytic amount of manganese(II) acetate tetrahydrate in dimethyl sulfoxide provide vinyl sulfones in very good yields. The use of DMSO as solvent and the presence of air are critical in achieving good yields.
N. Xue, R. Guo, X. Tu, W. Luo, W. Deng, J. Xiang, Synlett, 2016, 27, 2695-2698.

An electrocatalytic oxidation enables the construction of various (E)-vinyl sulfones directly from cinnamic acids and sodium sulfinates with high regioselectivity at room temperature via a sulfonyl radical intermediate.
P. Qian, M. Bi, J. Su, Z. Zha, Z. Wang, J. Org. Chem., 2016, 81, 4876-4882.

Regiospecific radical reactions of β-alkyl nitroalkenes with sulfonyl hydrazides provide allyl sulfones with high regioselectivity in the presence of dimethylformamide (DMF), whereas reactions in acetonitrile provide vinyl sulfones.
Y. Wang, G. Xiong, C. Zhang, Y. Chen, J. Org. Chem., 2021, 86, 4018-4026.

The synergistic interactions of the organic dye-type photocatalyst eosin Y, KI, and Cs2CO3 enable a decarboxylative cross-coupling reaction of cinnamic acids with sulfonylhydrazides under visible light irradiation using oxygen as the sole terminal oxidant to provide vinyl sulfones at room temperature.
S. Cai, Y. Xu, D. Chen, L. Li, Q. Chen, M. Huang, W. Weng, Org. Lett., 2016, 18, 2990-2993.

A metal-free room temperature decarboxylative cross-coupling between cinnamic acids and arylsulfonyl hydrazides provides (E)-vinyl sulfones. A regio- and stereoselective synthesis of 22 derivatives with diverse structural features has been achieved.
R. Singh, B. K. Allam, N. Singh, K. Kumari, S. K. Singh, K. N. Singh, Org. Lett., 2015, 17, 2656-2659.

An electrochemical oxidative N-S bond cleavage of aromatic sulfonylhydrazides, followed by cross-coupling reaction with cinnamic acids enable a stereoselective synthesis of (E)-vinyl sulfones in good yields with wide substrate scope under metal-free and halogen-free conditions.
Y. Zhao, Y.-L. Lai, K.-S. Du, D.-Z. Lin, J.-M. Huang, J. Org. Chem., 2017, 82, 9655-9661.

A copper-catalyzed aerobic decarboxylative sulfonylation of alkenyl carboxylic acids with sodium sulfinates offers an expedient strategy for stereoselective synthesis of (E)-alkenyl sulfones that are widely present in biologically active natural products and therapeutic agents. The transformation proceeds via a radical process and exhibits a broad substrate scope and good functional group tolerance.
Q. Jiang, B. Xu, J. Jia, A. Zhao, Y.-R. Zhao, Y.-Y. Li, N.-N. He, C.-C. Guo, J. Org. Chem., 2014, 79, 7372-7379.

An easily accessible, anion-functionalized ionic liquid, 1-ethyl-3-methylimidazolium (S)-2-amino-3-methylbutyric acid salt, [emim][Val], is an efficient additive for the CuI-catalyzed coupling reaction of sulfinic acid salts with aryl iodides, aryl bromides and vinyl bromides, leading to sulfones in good yields.
M. Bian, F. Xu, C. Ma, Synthesis, 2007, 2951-2956.

sing [Ir(COD)Cl]2 and a phosphoramidite ligand in the presence of DBU, trisubstituted vinyl sulfones could be synthesized from allyl sulfinates in high yields as exclusively E isomers.
Q.-L. Xu, L.-X. Dai, S.-L. You, Org. Lett., 2010, 12, 800-803.

An efficient synthesis of vinyl sulfones with commercially available sulfinic acid sodium salts and dibromides gave various phenyl and methyl vinyl sulfones in good yields, in the absence of any catalyst.
Z.-H. Guan, W. Zuo, L.-B. Zhao, Z.-H. Ren, Y.-M. Liang, Synthesis, 2007, 1465-1470.

An efficient synthesis of vinyl sulfones with commercially available sulfinic acid sodium salts and dibromides gave various phenyl and methyl vinyl sulfones in good yields, in the absence of any catalyst.
Z.-H. Guan, W. Zuo, L.-B. Zhao, Z.-H. Ren, Y.-M. Liang, Synthesis, 2007, 1465-1470.

A convenient copper-catalyzed radical reaction of readily available N-tosylhydrazones provides vinyl sulfones with excellent E stereoselectivity and broad substrate scope. An efficient one-pot synthesis of alkynes from N-tosylhydrazones has also been achieved.
S. Mao, Y.-R. Gao, X.-Q. Zhu, D.-D. Guo, Y.-Q. Wang, Org. Lett., 2015, 17, 1692-1695.

The cerium(IV) ammonium nitrate (CAN) mediated reaction of aryl sulfinates and sodium iodide with alkenes afforded vinyl sulfones in very good yields. Alkynes underwent a similar reaction to give β-iodovinyl sulfones, which on treatment with potassium carbonate afforded the corresponding acetylenic sulfones in high yields.
V. Nair, A. Augustine, T. D. Suja, Synthesis, 2002, 2259-2265.

Cs2CO3 promotes a a highly selective sulfonylation of 1,1-dibromo-1-alkenes with sodium sulfinates to provide (Z)-1-bromo-1-sulfonyl alkenes in good yields. A subsequent Sonogashira cross coupling gives selectively the corresponding sulfonylalkynyl alkenes.
M. Shiri, P. Salehi, Z. Mohammadpour, P. Salehi, B. Notash, Synthesis, 2021, 53, 1149-1156.

Copper powder catalyzes a syn-selective chlorosulfonylation of readily available alkynes by an atom transfer radical addition (ATAR) process to provide a broad range of (Z)-β-chlorovinylsulfones in good yields under mild conditions. This ligand-free method offers excellent stereoselectivity and high atom economy.
M. Zhang, W. Zhao, J. Ma, J. Li, Q. Meng, C. Shen, X. Zeng, Org. Lett., 2023, 25, 231-235.

(E)-β-Iodo vinylsulfones are synthesized in very good yields under ultrasound irradiation using alkynes, sulfonyl hydrazides, potassium iodide and hydrogen peroxide. The key features of this protocol are the speed and efficiency of the reactions.
C. Zhou, X. Zeng, Synthesis, 2021, 53, 4614-4620.

Halosulfonylation of terminal alkynes was achieved with sulfonylhydrazides as the sulfonyl precursor and inexpensive iron halide as halide source in the presence of TBHP to yield (E)-β-chloro and bromo vinylsulfones regio- and stereoselectively.
X. Li, X. Shi, M. Fang, X. Xu, J. Org. Chem., 2013, 78, 9499-9504.

The palladium-catalyzed reaction of sulfinic acid salts with a wide variety of aryl and vinyl halides or triflates, which is strongly influenced by the presence of nBu4NCl, provides unsymmetrical diaryl sulfones and aryl vinyl sulfones in good yields. The use of Xantphos, a rigid bidentate ligand with a wide natural bite angle, was found to be crucial for the success of the reaction.
S. Cacchi, G. Fabrizi, A. Goggiamani, L. M. Parisi, R. Bernini, J. Org. Chem., 2004, 69, 5608-5614.

A regio- and chemoselective sulfonylation of propargyl alcohols with sulfinamides in 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) provides straightforward and mild access to multi-substituted allenyl sulfones. This transformation was promoted by HFIP and did not require any catalysts or oxidants.
F.-F. Zou, Z. Luo, Y.-T. Yang, X. Zhuang, C.-M. Hong, Z.-Q. Liu, W.-F. Li, Q.-H. Li, T.-L. Liu, J. Org. Chem., 2022, 87, 15061-15070.

A TBHP/TBAI-mediated reaction of propargyl alcohols with sulfonyl hydrazides in the presence of HOAc provides allenyl sulfones in good yields in a short reaction time via HOAc-promoted sulfonohydrazide intermediate formation, sequential C-O, C-N, and N-S bond cleavage, and C-S bond formation. This reaction shows highly functional group compatibility and excellent regioselectivity.
Z. Yang, W.-J. Hao, S.-L. Wang, J.-P. Zhang, B. Jiang, G. Li, S.-J. Tu, J. Org. Chem., 2015, 80, 9224-9230.

A highly regioselective iodosulfonylation of allenes in the presence of CuI and 1,10-phenanthroline provides useful (E)-α-iodomethyl vinylsulfones in good yields under very mild conditions. This practical reaction is fast and operationally simple.
N. Lu, Z. Zhang, N. Ma, C. Wu, G. Zhang, Q. Liu, T. Liu, Org. Lett., 2018, 20, 4318-4322.

A sulfination of allenic carbonyl compounds provides a wide variety of vinylic sulfones in good yields in aqueous media under very mild conditions. This atom economic reaction offers wide functional group tolerance and a simple isolation by filtration for some products.
J. Goh, M. Maraswami, T.-P. Loh, Org. Lett., 2021, 23, 1060-1065.

A regio- and stereoselective copper-catalyzed sulfonylation of alkynyl imines with sulfonyl hydrazides provides a series of (E)-β-sulfonyl enones in good yields. Mechanistic studies suggest a radical process.
R. Chen, S. Li, J. Zhang, J. Cao, K.-K. Wang, T. Meng, L. Liu, J. Org. Chem., 2022, 87, 13322-13330.

A 1,2-thiocyanatosulfonation of terminal alkynes with NH4SCN and sulfonyl hydrazides provides (E)-β-(thiocyanato)vinyl sulfones via a radical pathway. This metal-free reaction offers mild conditions, readily available reagents, a broad substrate scope, good functional group compatibility, and excellent stereoselectivity.
M. Zhang, X. Zeng, Org. Lett., 2021, 23, 3326-3330.


Peterson reagents, in which alkyloxy groups on the silicon atom fix the conformation of the anion after treatment with Li-base, were reacted with a variety of aldehydes to give Z-α,β-unsaturated sulfones with high Z-selectivity in very good yields. For the reaction with aliphatic aldehydes, cyclopentyl methyl ether is the solvent of choice, while 1,2-dimethoxyethane gave higher selectivity for the reaction with aromatic aldehydes.
K. Ando, T. Wada, M. Okumura, H. Sumida, Org. Lett., 2015, 17, 6026-6029.

A manganese pincer complex catalyzes an unprecedented acceptorless dehydrogenative coupling of alkyl sulfones with alcohols to provide highly functionalized vinyl sulfones in good yields. Several functional groups including bromides and iodides are tolerated under the reaction conditions. This environmentally benign reaction produces dihydrogen and water as byproducts.
S. Waiba, M. K. Barman, B. Maji, J. Org. Chem., 2019, 84, 973-982.

Hydroboration with catecholborane, followed by treatment with easily available reagents such as alkenyl sulfones or alkynyl phenyl sulfones in the presence of a radical initiator, represents an effective and simple one-pot procedure for direct vinylation, formylation, and cyanation.
A.-P. Schaffner, V. Darmency, P. Renaud, Angew. Chem. Int. Ed., 2006, 45, 5847-5849.

Tetraphosphine cis,cis,cis-1,2,3,4-tetrakis[(diphenylphosphino)methyl]cyclopentane (Tedicyp) is an efficient ligand for the Heck reaction of sulfur-containing alkenes with aryl bromides. The rates and yields of the reactions strongly depend on the oxidation state of the sulfur atom.
A. Battace, T. Zair, H. Doucet, M. Santelli, Synthesis, 2006, 3495-3505.