Enantioselective cascade formal reductive insertion of allylic alcohols into the C(O)-C bond of 1,3-diketones: ready access to synthetically valuable 3-alkylpentanol units.

An unprecedented cascade reaction combining dual iron-amine-catalyzed enantioselective functionalization of allylic alcohols and chemoselective acyl transfer is presented. It allows, from diketones and allylic alcohols, preparation of efficiently functionalized γ-chiral alcohols in up to 96% yield and 96:4 er. The interest of this redox-, atom-, and step-economomical approach was further demonstrated in the short synthesis of several key fragments of biologically active natural products or odorant molecules.