Metal-free, one-pot highly selective synthesis of (E)-vinyl sulfones and sulfoxides via addition–oxidation of thiols with alkynes

Xue, Qicai; Mao, Zhijie; Shi, Yan; Mao, Haibin; Cheng, Yixiang; Zhu, Chengjian

doi:10.1016/j.tetlet.2012.01.135

Cited by 55 publications

(20 citation statements)

References 33 publications

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“…In 2012, Zhu and co-workers 35 disclosed a metal-free, highly selective approach to (E)-vinyl sulfones from hydrothiolation of alkynes (Scheme 17). It was the first example for the construction of vinyl sulfone scaffolds in one-pot by direct addition-oxidation of thiols with alkynes.…”

Section: Scheme 18 Synthesis Of (E)-vinyl Sulfones From Alkynes and Tmentioning

confidence: 99%

Recent advances in the synthesis of vinyl sulfones

2016

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Development of methodology for the preparation of vinyl sulfones is of significant interest to organic chemists. Recently, numerous useful methods have been developed, mainly including direct sulfonylation of olefins and alkynes, decarboxylative sulfonylation of α,β-unsaturated carboxylic acids and decomposition of tosylhydrazones. This review will focus on recent achievements in vinyl sulfones synthesis and the mechanisms of the reactions are also discussed.

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Section: Scheme 18 Synthesis Of (E)-vinyl Sulfones From Alkynes and Tmentioning

confidence: 99%

Recent advances in the synthesis of vinyl sulfones

2016

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“…Among the sulfur-containing structures, β-sulfonyl styrenes (styryl sulfones) have attracted much attention in different fields, resulting in various synthetic strategies for their applications, 1 especially in organic building blocks, 2 natural product synthesis, 3 bioactive molecules, 4 and functionalized emitter materials. 5 Conventional synthesis for this skeleton includes (1) oxidation of vinyl sulfides, 6 (2) elimination of halosulfones, 7 (3) Horner-Wadsworth-Emmons olefination of β-phosphonate sulfones with carbonyl compounds, 8 and (4) the addition of sulfonyl halides to alkynes. 9 In contrast to these traditional strategies, recent works have focused on various sulfonyl synthon-mediated cross-coupling of aryl substrates with a triple bond (for arylacetylenes), a double bond (for cinnamic acids, styryl bromides, boronic acids, or sulfides), and a single bond (for epoxides, dibromides) under versatile reagent-initiated conditions (e.g., transition metals, oxidants, bases, acids, salts, LEDs, solvents, or electrolytes).…”

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confidence: 99%

Gram-Scale Synthesis of β-Sulfonyl Styrenes

Chang

Hsiao

2018

Synthesis

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“…7 and addition-oxidation of thiols with alkynes. 8 We now report an approach to vinyl sulfoxides using sulfinyl chlorides 9-12 and olefins as starting materials.In our initial work, the reaction of styrene 1a with benzenesulfinyl chloride 2a did not occur. When DBU (1,.0] undec-7-ene) was added to the reaction mixture, however, the reaction did occur.…”

mentioning

confidence: 99%

“…Aromatic alkenes bearing substituents such as methyl or methoxy on the ring, underwent the reaction to provide the corresponding vinyl sulfones in good yields ( Table 2, entries 1-3, [8][9][10][11]. Moderate yields were observed for styrene bearing an α-alkyl substituent (Table 2, entries 4, 11).…”

mentioning

confidence: 99%

Synthesis of Vinyl Sulfoxides Using Sulfinyl Chlorides and Olefins

Ding

Wen²,

Wang

et al. 2015

Journal of Chemical Research

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Vinyl sulfoxides are useful building blocks in the synthesis of biologically active compounds. 1 There have been several methods for the synthesis of vinyl sulfoxides including the Wittig reaction, 2-3 the Horner-Wadsworth-Emmons reaction, 4 the Andersen reaction, 5 reduction of alkynyl sulfoxides, 6 oxidation of vinyl sulfides. 7 and addition-oxidation of thiols with alkynes. 8 We now report an approach to vinyl sulfoxides using sulfinyl chlorides 9-12 and olefins as starting materials.In our initial work, the reaction of styrene 1a with benzenesulfinyl chloride 2a did not occur. When DBU (1,.0] undec-7-ene) was added to the reaction mixture, however, the reaction did occur. The isolated product was identified by spectroscopy as [2-(phenylsulfonyl)vinyl]benzene (3a) instead of the targetted product, [2-(phenylsulfinyl)vinyl]benzene (4a). However, 4a could be obtained by the reaction of styrene (1a) with benzenesulfinyl chloride (2a) in the presence of ZnCl 2 followed by the treatment with DBU (Scheme 1). Inspired by these preliminary findings, we investigated the optimal conditions of this protocol for the synthesis of vinyl sulfoxides and vinyl sulfones. Firstly, a series of bases (e.g., DBU, Et 3 N, DABCO (1,4-diazabicyclo[2.2.2] octane), pyridine, etc.) was screened. Among them, DBU was the most effective, the other bases giving lower yields. Additionally, we found that 1a and 2a did not react in the absence of base. Various reaction conditions, such as solvents and temperature, were also examined for the optimum. Thus, the standard conditions for the synthesis of vinyl sulfoxides were established: treatment of the mixture obtained by the reaction of olefins with sulfinyl chlorides in the presence of ZnCl 2 at room temperature, with DBU as a scavenger in toluene under reflux produced vinyl sulfoxides. The intermediate saturated sulfoxide {4ab, [1-chloro-2-(phenylsulfinyl) ethyl]benzene} could be isolated from the reaction. This indicates that the reaction proceeds by ZnCl 2 -catalysed addition of sulfinyl chlorides to olefins followed by elimination with DBU to form vinyl sulfoxides.We investigated the scope of this protocol for the synthesis of vinyl sulfoxides. The results are listed in Table 1. It was discovered that a wide range of styrene derivatives can react to provide the corresponding vinyl sulfoxides in good yields (Table 1).In addition, an alternative method for the preparation of vinyl sulfones was provided by reaction of olefins with sulfinyl chlorides. The results are summarised in Table 2. A general method for synthesis of vinyl sulfoxides, using sulfinyl chlorides and olefins as starting materials and DBU as an HCl scavenger, has been developed. Vinyl sulfoxides were obtained from the ZnCl 2 catalysed addition of sulfinyl chlorides to olefins followed by the elimination with DBU. However, the direct reaction of sulfinyl chlorides with olefins in the presence of DBU, usually leads to generation of vinyl sulfones. The sulfonyl radicals generated from the DBU-mediated disproportionation of the s...

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Metal-free, one-pot highly selective synthesis of (E)-vinyl sulfones and sulfoxides via addition–oxidation of thiols with alkynes

Cited by 55 publications

References 33 publications

Recent advances in the synthesis of vinyl sulfones

Recent advances in the synthesis of vinyl sulfones

Gram-Scale Synthesis of β-Sulfonyl Styrenes

Synthesis of Vinyl Sulfoxides Using Sulfinyl Chlorides and Olefins

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