Synthesis of Organofluorine Compounds with Acylsilanes

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.

Visible-Light-Induced[4+1]Cyclization-Aromatization of Acylsilanes andα,β-Unsaturated Ketones

Herein we report the first[4+1]cyclization-aromatization reaction of acylsilanes andα,β-unsaturated ketones.The unprecedented visible-light-induced reaction proceeded through mild conditions without addition of any catalyst or additive,affording a variety of furans with broad substrate scope and good functional-group tolerance.The synthetic utility of the method was demonstrated by various downstream transformations of the otherwise difficult-to-access sulfone-containing silyl furans.The mechanism study reveals that 1,4-diketones are not likely to be the intermediates of the reaction.

Carbon-oxygen bond formation via visible-light-induced O-H insertion between acylsilanes and oximes

Visible light promoted C-O bond formation reaction through O-H insertion of acylsilanes with oximes has been developed.The reaction occurred under mild reaction conditions(sole blue LED irradiation in the absence of any catalysts or additives)with a short reaction time and afforded the corresponding oxime ethers in moderate to good yields.

Silicon-mediated enantioselective synthesis of structurally diverseα-amino acid derivatives

The catalytic asymmetric synthesis of novel and chiral amino acid derivatives with unconventional chemo-,diastereo-,and enantio-selectivity remains a paramount challenge.Herein we reported a novel protocol for the use of highly enantioselective copper-catalyzed cycloaddition ofα,β-unsaturated acylsilanes as a springboard reaction for the facile synthesis of structurally diversified pyrrolidines and complicatedα-amino esters by desilylation.The newly developed process could provide a wide range of synthetically useful acylsilane-substituted pyrrolidines(ASiP)in high yields and excellent diastereo-and enantioselectivities with Cu/(R)-XylBINAP complex as the catalyst.And the downstream desilylation transformation enables to expand the potntial applications of 1,3-dipolar cycloaddition in the construction of structurally unique amino acid derivatives,in which an unprecedented and concerted fluoride anion-promoted C–X(X=H,Si,N,C)bond cleavage occurred to the enantioselective construction of aldehyde-substituted pyrrolidines,linear cinnamaldehyde or alkene-substituted amino esters in high ee values.