As the cross-coupling needs of chemists continue to grow for accessing increasingly complex targets,radical-based transformations have become mainstay methodologies for the discovery of new reactivity under mild and w...As the cross-coupling needs of chemists continue to grow for accessing increasingly complex targets,radical-based transformations have become mainstay methodologies for the discovery of new reactivity under mild and wastelimiting conditions.En route to such methodological advancements,the observation of the 1,2-boron shift a novel radical rearrangement in its application has generated a new cross-coupling methodology to access products that were previously inaccessible or otherwise cumbersome to make.The origins of this radical rearrangement along with the synthetic applications to organic chemistry are highlighted.展开更多
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
文摘As the cross-coupling needs of chemists continue to grow for accessing increasingly complex targets,radical-based transformations have become mainstay methodologies for the discovery of new reactivity under mild and wastelimiting conditions.En route to such methodological advancements,the observation of the 1,2-boron shift a novel radical rearrangement in its application has generated a new cross-coupling methodology to access products that were previously inaccessible or otherwise cumbersome to make.The origins of this radical rearrangement along with the synthetic applications to organic chemistry are highlighted.
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.
