Remote Stereocontrol of All-Carbon Quaternary Centers via Cobalt-Catalyzed Asymmetric Olefin Isomerization  

作　　者：Xianle Rong Jie Yang Shihan Liu Yu Lan Qiang Liu 

机构地区：[1]Engineering Research Center of Advanced Rare Earth Materials,Ministry of Education,Department of Chemistry,Tsinghua University,Beijing 100084 [2]Chongqing Key Laboratory of Theoretical and Computational Chemistry,School of Chemistry and Chemical Engineering,Chongqing University,Chongqing 400030 [3]Institute of Green Catalysis,College of Chemistry,Zhengzhou University,Zhengzhou,Henan 450001 [4]Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs,Shanghai Jiao Tong University,Shanghai 200240

出　　处：《CCS Chemistry》2023年第6期1293-1300,共8页中国化学会会刊（英文）

基　　金：We gratefully acknowledge funding from the National Key R&D Program of China(grant no.2021YFF0701600);the National Natural Science Foundation of China(grant nos.22171159 and 22225103).

摘　　要：Asymmetric olefin isomerization has become a powerful tool for positional migration of C=C double bonds to afford valuable chiral olefins.However,the synthesis of optically active all-carbon quaternary stereocenters via this strategy is still rare.Herein,we report a cobaltcatalyzed desymmetric olefin isomerization to access 1-methylcyclohexenes bearingβ-quaternary stereocenters in a chemo-,site-,and stereoselective fashion.Preliminary mechanistic studies have revealed the Co-H insertion/β–Helimination reaction pathway and the origin of remote stereocontrol of all-carbon quaternary centers.The gram-scale synthesis and stereoretentive transformations of spirocyclic products demonstrate the synthetic utility of this reaction.

关 键 词：olefin isomerization remote stereocontrol all-carbon quaternary stereocenter cobalt catalysis chiral cyclohexene 

分 类 号：O62[理学—有机化学]