The Linkage of Sulfonimidoyl Fluorides and Unactivated Alkenes via Hydrosulfonimidoylation

作     者：Daming Zeng Yinhao Ma Prof. Dr. Wei-Ping Deng Dr. Ming Wang Prof. Dr. Xuefeng Jiang 

作者机构：Shanghai Key Laboratory of Green Chemistry and Chemical Process School of Chemistry and Molecular Engineering East China Normal University 3663 North Zhongshan Rd. Shanghai 200062 P. R. China School of Pharmacy and Shanghai Key Laboratory of New Drug Design East China University of Science and Technology Shanghai 200237 P. R. China State Key Laboratory of Elemento-Organic Chemistry Nankai University Tianjin 300071 P. R. China Institute of Eco-Chongming Shanghai 202162 P. R. China 

出 版 物：《Angewandte Chemie》 

年 卷 期：2022年第134卷第44期

学科分类：081704[工学-应用化学] 08[工学] 0817[工学-化学工程与技术] 

主　　题：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.