Cobalt(Ⅲ)hydride HAT mediated enantioselective intramolecular hydroamination access to chiral pyrrolidines  

作　　者：Qi Meng Tao Qin Huanran Miao Ge Zhang Qian Zhang 

机构地区：[1]Jilin Province Key Laboratory of Organic Functional Molecular Design&Synthesis,Department of Chemistry,Northeast Normal University,Changchun,130024,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6期2002-2008,共7页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(22171043,22193012,221831002);the Fundamental Research Funds for the Central Universities-Excellent Youth Team Program(2412023YQ001);Ten Thousand Talents Program for generous financial support。

摘　　要：Enantioenriched pyrrolidines and derivatives are ubiquitous substructures in compounds of importance to medicinal and biological chemistry.Herein,we report an efficient cobalt-catalyzed intramolecular asymmetric hydroamination reaction that produces chiral pyrrolidines with good to excellent yield and enantiocontrol.Compared with previously reported radicalinvolved methodologies for enantioenriched pyrrolidines,these conditions feature two elegant versatilities,enabling(1)the use of cobalt-catalyzed hydrogen atom transfer(HAT)to generate organocobalt intermediates that bring radical reaction to organometallic chemistry,and(2)enantioselective intramolecular C-N bond forging through an S_(N)2-like displacement involving dynamic kinetic resolution(DKR).This approach provides a new alternative and efficient methodology for enantioselective radical-involved C-N bond construction that can be used in the synthesis of both chiral pyrrolidines and homologous nitrogen heterocycles.

关 键 词：asymmetric catalysis radical hydroamination cobalt catalysis hydrogen atom transfer 

分 类 号：O626.13[理学—有机化学]