Construction of axial and point chirality through Ni-catalyzed sila-cycloaddition reaction via desymmetrization and(dynamic)kinetic resolution

作     者：Hua-Jie Zhu Ming-Hao Shen Jia-Wei Si Wei-Ke Zhu Xiao-Jun Fang Fei Ye Jian Cao Zheng Xu Li-Wen Xu 

作者机构：Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education and Key Laboratory of Organosilicon Material Technology of Zhejiang Province College of Material Chemistry and Chemical Engineering Hangzhou Normal University State Key Laboratory for Oxo Synthesis and Selective Oxidation Suzhou Research Institute Lanzhou Institute of Chemical PhysicsChinese Academy of Sciences 

出 版 物：《Science China Chemistry》 (中国科学:化学(英文版))

年 卷 期：2025年第68卷第6期

页      面：2513-2523页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：supported by the National Natural Science Foundation of China (22072035, 22361162606, 22371060) the Zhejiang Provincial Natural Science Foundation of China (LZ23B020002, LY22B020006, LR22B020002) the Special Support Program for High-level Talents of Zhejiang Province (2021R51005) the Hangzhou Science and Technology Bureau (TD2020015) 

主　　题：atropisomers silicon-stereogenic center desymmetrization (dynamic) kinetic resolution point chirality 

摘      要：Recent developments in chirality chemistry have revealed remarkable instances of atropisomers featuring multiple chiral elements. Despite significant progress in the synthesis and application of atropisomers, developing a synthetic protocol for the simultaneous introduction of axial and point chirality is still a fascinating challenge. In this context, we present a convenient and versatile method for synthesizing novel atropisomers with axial and point chirality. This approach, based on a new reaction mechanism with nickel-controlled Si–C bond activation, facilitates the controllable migratory insertion of aldehydes into the Ni–C bond. We utilize multidimensional strategies of desymmetrization, kinetic resolution and dynamic kinetic resolution to complete enantioselective nickel-catalyzed ring expansion of benzosilacyclobutenes with aldehydes. The design of multidimensional kinetic resolution, desymmetrization, and dynamic resolution, features a straightforward catalytic system, mild reaction conditions, and broad functional group tolerances. Various axially chiral biaryl oxasilacycles bearing carbon-or siliconstereogenic centers are obtained with excellent diastereo-and enantio-selectivities(up to 20:1 dr and 99.9% ee) through the use of a chiral Ni complex with a large cavity-type 1,1,4,4-tetra-aryl-2,3-O-isopropylidene-L-threitol(TADDOL)-derived phosphoramidite ligand.