Copper-catalyzed enantioselective desymmetrizing C(sp^(2))-H functionalization of azide-ynamides via α-imino copper carbenes  

作　　者：En-He Huang Li-Gao Liu You-Wei Yin Hao-Xuan Dong Ji-Jia Zhou Xin Lu Bo Zhou Long-Wu Ye 

机构地区：[1]Key Laboratory for Chemical Biology of Fujian Province and State Key Laboratory of Physical Chemistry of Solid Surfaces,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,China [2]State Key Laboratory of Organometallic Chemistry,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,Shanghai 200032,China

出　　处：《Science China Chemistry》2024年第9期2982-2988,共7页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(22331004,22125108 and 22121001);the National Fund for Fostering Talents of Basic Science NFFTBS(J1310024)。

摘　　要：α-Imino metal carbenes are versatile intermediates in organic synthesis,and have broad applications in the assembly of divergent N-heterocycles.However,the catalytic enantioselective desymmetrization based onα-imino metal carbenes has not been developed to date.Herein,we disclose an enantioselective desymmetrizing C(sp^(2))-H functionalization of azide-ynamides viaα-imino copper carbenes,leading to the efficient assembly of divergent chiral indoloazepines in generally moderate to excellent yields with high enantioselectivities.Notably,this reaction represents the first enantioselective desymmetrization based onα-imino metal carbenes.Further synthetic transformations and biological tests show the potential utility of this method.Moreover,computational studies are employed to elucidate the reaction mechanism and the origin of enantioselectivity.

关 键 词：enantioselective desymmetrization metal carbenes copper catalysis nitrene transfer alkynes 

分 类 号：O621.251[理学—有机化学]