中心手性金属铑配合物催化的不对称光诱导Giese自由基加成反应  

Asymmetric Photoinduced Giese Radical Addition Enabled by a Single Chiral-at-Metal Rhodium Complex

作　　者：陈亮 胡良建 杜宇 苏伟平[1] 康强 Chen Liang;Hu Liangjian;Du Yu;Su Weiping;Kang Qiang(State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002;University of Chinese Academy of Sciences,Beijing 100049;College of Material Engineering,Fujian Agriculture and Forestry University,Fuzhou 350002)

机构地区：[1]中国科学院福建物质结构研究所结构化学国家重点实验室,福州350002 [2]中国科学院大学,北京100049 [3]福建农林大学材料工程学院,福州350002

出　　处：《有机化学》2020年第11期3944-3952,M0014,共10页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金面上(No.21871261)资助项目.

摘　　要：报道了一种可见光驱动的双功能中心手性金属铑配合物催化的不对称自由基加成反应,由对胺基苯乙酸生成的对胺基苄基自由基对α,β-不饱和酰基咪唑进行立体选择性的1,4-加成,以中高收率和高对映选择性合成了一系列加成产物.该反应具有对映选择性高、反应条件温和、操作简单等特点.根据对双功能中心手性金属配合物催化的研究和文献报道,提出了一个合理的反应机理.A visible-light driven asymmetric Giese radical addition catalyzed by a bifunctional chiral-at-metal rhodium complex has been developed.para-Aminobenzyl radicals generated from para-aminophenylacetic acids could undergo a 1,4-addition in a highly enantioselective approach toα,β-unsaturated 2-acyl imidazoles,and a variety of corresponding adducts were obtained in moderate to high yields with excellent enantioselectivities.This reaction features high enantioselectivity,mild reaction conditions and an operationally simple procedure.A plausible reaction mechanism is proposed based on our research and literature precedents on dual functional chiral-at-metal catalysis.

关 键 词：可见光催化 双功能手性铑配合物 Giese自由基加成反应 对胺基苄基自由基 

分 类 号：O641.4[理学—物理化学] O621.251[理学—化学]