Ni-Catalyzed Enantioselective Difunctionalization of Alkynes to Azepine Derivatives Bearing a Quaternary Center and an Unprotected Imine  

作　　者：Jian Long Zhiwu Lu Xiao-Lin Li Peng Xue Wen-Bo Liu 

机构地区：[1]Engineering Research Center of Organosilicon Compounds&Materials(Ministry of Education)and College of Chemistry and Molecular Sciences,Wuhan University,Wuhan,Hubei,430072 China

出　　处：《Chinese Journal of Chemistry》2024年第8期873-878,共6页中国化学（英文版）

基　　金：supported by NSFC(22222111,21971198,and 22371215);National Key R&D Program of China(2022YFA1502902);Large-scale Instrument and Equipment Sharing Foundation of Wuhan University.Dr.Zhiwu Lu thanks China Postdoctoral Science Foundation(2022M712458)for the financial support.

摘　　要：Comprehensive Summary,The azepine ring is a prominent structural scaffold in biologically significant molecules. In this study, we present a Ni(II)-catalyzed asymmetric difunctionalization of alkynes, involving intermolecular regioselective arylation and intramolecular nitrile addition, enabling the synthesis of enantioenriched azepine derivatives. This reaction simultaneously installs an all-carbon quaternary stereocenter and introduces an unprotected imine functionality, showing great promise for subsequent transformations. The reaction exhibits good tolerance toward various functional groups, resulting in high yields and enantioselectivities. The synthetic utility of this methodology is further demonstrated through gram-scale synthesis and product derivatization. This research offers an efficient approach to the synthesis of seven-membered nitrogen heterocycles.

关 键 词：Nickel Asymmetric catalysis N-HETEROCYCLES Alkyne functionalization Quaternary centers 

分 类 号：O62[理学—有机化学]