Rhodium-Catalyzed Regio- and Enantioselective Direct Allylation of Methyl Ketones

Abstract

AbstractWe report a highly branch-selective and enantioselective allylic alkylation of simple ketones with racemic aliphatic allylic carbonates under mild conditions. By using a Rh–bisoxazolinephosphine system and catalytic amounts of a base in THF, a series of chiral β-branched γ,δ-unsaturated ketones were obtained with excellent regio- and enantioselectivities. An outer-sphere nucleophilic substitution C–C bond-formation process is proposed on the basis of mechanistic studies.