Photocatalytic C(sp^(3))-H gem-Difluoroallylation and Alkylation with Alkenes via a Base-Assisted Formal 1,2-Hydrogen Atom Transfer of Amidyl Radicals  

作　　者：Meifang Tang Bingbing Feng Yanyang Bao Zhongtian Xu Chao Huang Hanliang Zheng Gangguo Zhu Yanan Wang Zheliang Yuan 

机构地区：[1]Key Laboratory of the Ministry of Education for Advanced Catalysis Materials,College of Chemistry and Materials Sciences,Zhejiang Normal University,688 Yingbin Road,Jinhua,Zhejiang 321004,China

出　　处：《Chinese Journal of Chemistry》2024年第18期2203-2210,共8页中国化学（英文版）

基　　金：We thank the National Natural Science Foundation of China(22001233);Zhejiang Provincial Ten Thousand Talent Program(2020R52021)and Zhejiang Normal University for financial support.

摘　　要：Compared to well-established 1,5-HAT of N-centered radicals,the synthetic applications of 1,2-HAT process were scarce due to the high barrier and constrained three-membered transition state.Here,we have developed a novel C(sp')-H gem-difluoroallylation via a base assisted formal 1,2-HAT of amidyl radicals with the reductive quenching cycle of photocatalyst.This transformation enables the efficient formation ofα-aminoalkyl radicals via 1,2-HAT and showcases good functional group tolerance.Our preliminary mechanistic experiments,along withDensity Functional Theory(DFT)calculations demonstrate thefeasibility of 1,2-HAT of amidyl radicals,especially when assisted by a base.Furthermore,our method also succeeds in the Giese addition of electron-deficient alkenes as well as styrene.

关 键 词：1 2-Hydrogen atom transfer Amidyl radicals gem-Difluoroallylation ALKENES Photocatalysis Defluoroalkylation 

分 类 号：O62[理学—有机化学]