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 no...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.展开更多
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.
文摘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.
