Asymmetric Allylic Alkylation of Alkanoic‐Acid Ester Enolates

A protocol for the direct palladium‐catalyzed asymmetric allylic alkylation of simple alkanoic‐acid esters through their lithium enolates has been developed. The method permits to create stereogenic centers in the homo‐allylic or allylic position. The configuration of the allylation products has been elucidated. The palladium‐catalyzed enantioselective allylic alkylation of nonstabilized lithium enolates is a long‐standing problem in asymmetric syntheses. A protocol based upon suitable reaction conditions and appropriate ligands enables the asymmetric allylation of alkanoic‐acid esters through their lithium enolates in a direct manner that does not require detours via ester surrogates. Thus, stereogenic centers can be created either in allylic or homo‐allylic position.