Difluoroenoxysilanes in Catalytic Asymmetric Allylic Alkylation

An allylic substitution with difluoroenoxysilanes as the nucleophile is accomplished for the enantioselective synthesis of α-allylic α,α-difluoroketones. With racemic branched allylic alcohols as the easily accessible allylic electrophile, this branched-selective and enantioconvergent allylic alkylation reaction is catalyzed by an Ir(I)/(<i>P</i>,olefin) complex and overcomes the low nucleophilicity of difluoroenoxysilanes to furnish β-chiral α,α-difluoroketones in moderate to good yields with high enantioselectivity (up to >99.9:0.1 er).