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...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.展开更多
基金supported by the National Natural Science Foundation of China(22001065)the Science and Technology Foundation of Hunan Province(2021JJ30090)+3 种基金Guangdong Provincial Key Laboratory of Catalysis(2020B121201002)Shenzhen Science and Technology Program(KQTD20210811090112004)supported by Center for Computational Science and Engineering at SUSTechthe CHEM high-performance supercomputer cluster(CHEM-HPC)located at the Department of Chemistry,SUSTech。
文摘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.
