文献类型：期刊文献

英文题名：The Linkage of Sulfonimidoyl Fluorides and Unactivated Alkenes via Hydrosulfonimidoylation

作者：Zeng, Daming[1,2,3];Ma, Yinhao[1];Deng, Wei-Ping[2,3];Wang, Ming[1];Jiang, Xuefeng[1,4,5]

机构：[1]East China Normal Univ, Sch Chem & Mol Engn, Shanghai Key Lab Green Chem & Chem Proc, 3663 North Zhongshan Rd, Shanghai 200062, Peoples R China;[2]East China Univ Sci & Technol, Sch Pharm, Shanghai 200237, Peoples R China;[3]East China Univ Sci & Technol, Shanghai Key Lab New Drug Design, Shanghai 200237, Peoples R China;[4]Nankai Univ, State Key Lab Elementoorgan Chem, Tianjin 300071, Peoples R China;[5]Inst Ecochongming, Shanghai 202162, Peoples R China

年份：2022

卷号：61

期号：44

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20224112861946);WOS:【SCI-EXPANDED(收录号:WOS:000863957300001)】；

基金：The authors are grateful for financial support provided by NSFC (22125103, 22071057, 21971065 and 21871089), STCSM (22JC1401000, 20XD1421500 and 20JC1416800), and the Fundamental Research Funds for the Central Universities.

语种：英文

外文关键词：Alkene; Hydride Transfer; Hydrosulfonimidoylation; Linkage; Sulfonimidoyl Fluoride

摘要：Sulfur(VI) fluoride cleavage and exchanging linkage, a new generation of linkage chemistry, exhibits enormous potential for combining a range of functional molecules in an increasing number of fields. Herein, we established a metal-free linkage of unactivated alkenes and sulfonimidoyl fluorides via hydrosulfonimidoylation to construct sulfoximines within minutes. An intermolecular hydride transfer process is the key step, and it occurs via overlap of the LUMO in the sulfonimidoyl cation and HOMO in the unactivated alkene, which was confirmed via control experiments with deuterated compounds. DFT calculations further demonstrated the concerted process involving formation of the S-C(sp(3)) bond and hydride transfer. Remarkably, abundant natural products and pharmaceuticals with multiple heteroatoms and sensitive functional groups have been subjected to the current linkage reaction to achieve various sulfoximine linkages, furnishing the basis for drug discovery and drug conjugation.