文献类型：期刊文献

英文题名：Divergent sulfur(VI) fluoride exchange linkage of sulfonimidoyl fluorides and alkynes

作者：Zeng, Daming[1,2,3];Ma, Yinhao[1];Deng, Wei-Ping[2,3];Wang, Ming[1];Jiang, Xuefeng[1,4]

机构：[1]East China Normal Univ, Sch Chem & Mol Engn, Shanghai Key Lab Green Chem & Chem Proc, Shanghai, Peoples R China;[2]East China Univ Sci & Technol, Sch Pharm, Shanghai, Peoples R China;[3]East China Univ Sci & Technol, Shanghai Key Lab New Drug Design, Shanghai, Peoples R China;[4]Nankai Univ, State Key Lab Elemento Organ Chem, Tianjin 300071, Peoples R China

年份：2022

卷号：1

期号：6

起止页码：455

外文期刊名：NATURE SYNTHESIS

收录：WOS:【ESCI(收录号:WOS:001125269900005)】；

基金：We are grateful for financial support provided by NSFC (22125103, 22071057 and 21871089), STCSM (20XD1421500 and 20JC1416800), and the Fundamental Research Funds for the Central Universities.

语种：英文

摘要：Sulfur(VI) fluoride exchange reactions have been applied to the linkage of a diverse range of molecules. However, the connectivity of fluorosulfuryls with alkynes remains a formidable challenge owing to the high reactivity of pi systems. Here, we report a divergent sulfur(VI) fluoride exchange reaction between sulfonimidoyl fluorides and alkynes to afford vinylic and acetylenic sulfoximines. Experimental and computational mechanistic studies elucidated key BF3-bridged six-membered transition states that enabled the synchronous activation of silicon-capped alkynes and sulfonimidoyl fluorides via the interactions of F center dot center dot center dot Si and B center dot center dot center dot F. Mechanistic studies also revealed that N-benzyl sulfonimidoyls undergo a 1,5-hydrogen migration from the benzylic position to the acetylenic position, which generates the observed vinylic sulfoximines. A range of synthetic transformations, which include azide-alkyne cycloadditions were demonstrated on the vinylic and acetylenic sulfoximine products. The coupling of sulfonimidoyl fluorides and alkynes using sulfur(VI) fluoride exchange (SuFEx) reactions has not been available because of the intrinsic reactivity of the pi component. Now, a divergent SuFEx process between sulfonimidoyl fluorides and alkynes to produce vinylic or acetylenic sulfoximines is reported. Mechanistic studies reveal the origins of the vinylic sulfoximines, and several synthetic transformations of the products demonstrate the utility of the process.