Construction of remote cyano-substituted quaternary carbon centers via nickel-catalyzed migratory hydrocyanation of unconjugated dienes  

作　　者：Yidan Xing Rongrong Yu Mingdong Jiao Ting Wang Xianjie Fang 

机构地区：[1]Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education,Key Laboratory of Organosilicon Material Technology of Zhejiang Province,College of Material,Chemistry and Chemical Engineering,Hangzhou Normal University,Hangzhou 311121,China [2]Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs,School of Chemistry and Chemical Engineering,Shanghai Jiao Tong University,Shanghai 200240,China

出　　处：《Science China Chemistry》2024年第10期3397-3405,共9页中国科学（化学英文版）

基　　金：the National Natural Science Foundation of China(22278265,U22B20137 and 22203069);the Zhejiang Provincial Natural Science Foundation of China(LR24B020002);the start-up funding from Hangzhou Normal University(4095C50222204165 and 4095C50223204074);the Interdisciplinary Research Project of Hangzhou Normal University(2024JCXK04)for financial support of this research。

摘　　要：The transition-metal-catalyzed migratory functionalization has emerged as a robust protocol for the building of C–C bonds remote from the“initiation”position.However,a similar strategy for the construction of quaternary carbon centers is still underdeveloped and only a limited number of reports exist.Herein,we report a nickel-catalyzed migratory hydrocyanation of unconjugated dienes to construct remote cyano-substituted quaternary carbon centers.This transformation features exceptional regioselectivity,mild reaction conditions,broad substrate scope and high yields.The synthetic utility of this method has been highlighted by a series of product derivatizations,and the potential of this transformation has been extended to synthesize TRPV1 antagonist and the key intermediate in the total synthesis of quebrachamine.Density functional theory(DFT)studies unveiled that the specific catalytic pocket assumed a significant role in the selective formation of cyano-substituted quaternary carbon centers.

关 键 词：chain-walking regioselectivity remote cyanation quaternary carbon centers unconjugated dienes 

分 类 号：O621.251[理学—有机化学]