Organic Chemistry Portal
Reactions > Organic Synthesis Search

Categories: C-S Bond Formation > Synthesis of sulfones >

Vinyl sulfones

Recent Literature


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.


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.


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.


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.


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.


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.


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.


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.


U
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.


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.


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.

Related


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.


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.