Cu/chiral phosphoric acid-catalyzed radical-initiated asymmetric aminosilylation of alkene with hydrosilane  

作　　者：Yang Zeng Xiao-Dong Liu Xian-Qi Guo Qiang-Shuai Gu Zhong-Liang Li Xiao-Yong Chang Xin-Yuan Liu 

机构地区：[1]Shenzhen Grubbs Institute,Southern University of Science and Technology,Shenzhen 518055,China [2]Academy for Advanced Interdisciplinary Studies,Southern University of Science and Technology,Shenzhen 518055,China [3]Department of Chemistry,Southern University of Science and Technology,Shenzhen 518055,Chin

出　　处：《Science China Chemistry》2019年第11期1529-1536,共8页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(21722203,21831002,21801116,21572096);Shenzhen Special Funds for the Development of Biomedicine,Internet,New Energy,and New Material Industries(JCYJ20170412152435366,JCYJ20170307105638498,JCYJ20180302180235837);Guangdong Natural Science Foundation(2018A030310083);Shenzhen Nobel Prize Scientists Laboratory Project(C17783101)

摘　　要：The catalytic radical-initiated asymmetric 1,2-aminosilylation of alkene with a hydrosilane under Cu(I)/CPA cooperative catalysis has been developed.This method features the use of hydrosilane as the reductive radical precursor,enabling efficient access to skeletally diverse silicon-containing azaheterocycles including pyrrolidine,indoline and isoindoline bearing anα-tertiary stereocenter with high enantioselectivity.The key to the success includes the use of Cu(I)/CPA cooperative catalyst system and theβ-silicon effect of the silyl group to stabilize the in situ generated carbocation intermediate.The catalytic radical-initiated asymmetric 1,2-aminosilylation of alkene with a hydrosilane under Cu(I)/CPA cooperative catalysis has been developed. This method features the use of hydrosilane as the reductive radical precursor, enabling efficient access to skeletally diverse silicon-containing azaheterocycles including pyrrolidine, indoline and isoindoline bearing an α-tertiary stereocenter with high enantioselectivity. The key to the success includes the use of Cu(I)/CPA cooperative catalyst system and the β-silicon effect of the silyl group to stabilize the in situ generated carbocation intermediate.

关 键 词：ASYMMETRIC RADICAL chemistry aminosilylation alkenes Cu/chiral phosphoric acid silyl RADICAL 

分 类 号：O62[理学—有机化学]