Asymmetric Alkynylation of Tertiary Carbon-Centered Radical via Copper-Catalyzed Radical Relay  

作　　者：Dunqi Wu Lianqian Wu Pinhong Chen Guosheng Liu 

机构地区：[1]Chang-Kung Chuang Institute,East China Normal University,3663 North Zhongshan Road,Shanghai 200062,China [2]State Key Laboratory of Organometalic Chemistry,and Shanghai Hongkong Joint Laboratory in Chemical Synthesis,Center for Excellence in Molecular Synthesis,Shanghai Institute of Organic Chemistry,University of Chinese Academy of Sciences,Chinese Academy of Sciences,345 Lingling Road,Shanghai 200032,China

出　　处：《Chinese Journal of Chemistry》2022年第14期1699-1704,共6页中国化学（英文版）

基　　金：financial support from the National Key R&D Program of China(No.2021YFA1500100);the National Na-ture Science Foundation of China(Nos.91956202,21790330,and 21821002);the Science and Technology Commission of Shanghai Municipality(NoS.20JC1417000,21520780100,and19590750400);the Key Research Program of Frontier Science(QYZDJSSW-SLH055);the International Partnership Program(121731KYSB20190016)of the Chinese Academy of Sciences.

摘　　要：Alkynes are frequently found in a high proportion of natural products and bioactive moleculars,as well as a common synthon in organic synthesis,which can be easily transformed to an alkenyl,alkyl,heteroaryl,or carboxylic acid group.The enantioselective construction of alkyne substituted all carbon quaternary stereocenters is rarely reported and still a big challenge.As part of our continuous effort on developing asymmetric radical transformations,we found introducing an amidyl group(CONHAr)adjacent to the tertiary carbon radical could enable the asymmetric radical coupling with alkyne reagents.The amidyl group may stabilize the tertiary carbon radical or coordination with the chiral copper catalyst.Herein,we communicate a copper-catalyzed asymmetric trifluoromethyl-alkynylation ofα-aryl substituted acrylamides,which provides a straightforward and efficient access to chiral quaternary all-carbon centers bearing alkynyl groups in good yields and enantioselectivities.This reaction was also applied for the synthesis of chiral functionalized dipeptide.

关 键 词：Copper Asymmetric catalysis Asymmetric alkynylation Chiral quaternary carbon stereocenters RADICALS 

分 类 号：O62[理学—有机化学]