Comprehensive Summary,Organofluorine compounds are central in synthetic chemistry,medicinal chemistry and material chemistry.In this review,we summarize the investigations on the synthesis of organofluorine compounds ...Comprehensive Summary,Organofluorine compounds are central in synthetic chemistry,medicinal chemistry and material chemistry.In this review,we summarize the investigations on the synthesis of organofluorine compounds with acylsilanes.For the non-fluorinated acylsilanes,the in situ generation of difluoroenoxysilanes from the reactions of the acylsilanes with trifluoromethylation reagents is the major pathway,leading to the facile preparation of variousα,α-difluoroketones.For the fluoroalkylacylsilanes,apart from the in situ generation of difluoroenoxysilanes through anion Brook rearrangement,radical Brook rearrangement of the photoexcited acylsilanes and the selective control of reactivities of the biradicals pave the way for the synthesis of a variety of organofluorine compounds.In general,most of these reactions gave racemic products,and the asymmetric synthesis of organofluorine compounds with acylsilanes is still rare,which would be a future.展开更多
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financial support from the National Key R&D Program of China(2022YFA1506100)Fundamental Research Funds for the Central Universities(2042023kf1010,2042023kf0202).
文摘Comprehensive Summary,Organofluorine compounds are central in synthetic chemistry,medicinal chemistry and material chemistry.In this review,we summarize the investigations on the synthesis of organofluorine compounds with acylsilanes.For the non-fluorinated acylsilanes,the in situ generation of difluoroenoxysilanes from the reactions of the acylsilanes with trifluoromethylation reagents is the major pathway,leading to the facile preparation of variousα,α-difluoroketones.For the fluoroalkylacylsilanes,apart from the in situ generation of difluoroenoxysilanes through anion Brook rearrangement,radical Brook rearrangement of the photoexcited acylsilanes and the selective control of reactivities of the biradicals pave the way for the synthesis of a variety of organofluorine compounds.In general,most of these reactions gave racemic products,and the asymmetric synthesis of organofluorine compounds with acylsilanes is still rare,which would be a future.
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.
