Strain-promoted S-arylation and alkenylation of sulfinamides using arynes and cyclic alkynes  

作　　者：Xi Zou Boming Shen Gao-lin Li Qian Liang Yanhua Ouyang Binghe Yang Peiyuan Yu Bing Gao 

机构地区：[1]State Key Laboratory of Chemo/Bio-Sensing and Chemometrics,College of Chemistry and Chemical Engineering,Institute of Chemical Biology and Nanomedicine,Hunan University,Changsha 410082,China [2]Department of Chemistry and Shenzhen Grubbs Institute,Guangdong Provincial Key Laboratory of Catalysis,Southern University of Science and Technology,Shenzhen 518055,China

出　　处：《Science China Chemistry》2024年第3期928-935,共8页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(22001065);the Science and Technology Foundation of Hunan Province(2021JJ30090);Guangdong Provincial Key Laboratory of Catalysis(2020B121201002);Shenzhen Science and Technology Program(KQTD20210811090112004);supported by Center for Computational Science and Engineering at SUSTech;the CHEM high-performance supercomputer cluster(CHEM-HPC)located at the Department of Chemistry,SUSTech。

摘　　要：The conversion of commercially available chiral sulfinamides into pharmaceutically useful chiral sulfoximines via direct SIVfunctionalization is synthetically attractive but challenging due to the competitive reaction of N-functionalization. Herein, we disclose a novel strain-release strategy to access stereospecific and chemoselective SIV-arylation and alkenylation of sulfinamides using arynes and strained cyclic alkynes. This method tolerates an unprecedented chemical diversity of functional groups attached to the nitrogen center(N-R). The origin of the high SIV-selectivity is elucidated by density functional theory calculations, suggesting a stepwise mechanism for the aryne substrates and a concerted mechanism for the cyclic alkynes.

关 键 词：ARYLATION ALKENYLATION SULFOXIMINES sulfinamides ARYNES 

分 类 号：O623.8[理学—有机化学]