First Example of the Intermolecular Palladium‐Catalyzed Asymmetric Allylic Alkylation of Hydroxyacrylates: Synthesis of All‐Carbon α‐Aryl Quaternary Aldehydes

Abstract

AbstractA set of acyclic all‐carbon α‐aryl quaternary aldehydes was synthesized by intermolecular palladium‐catalyzed asymmetric allylic alkylation (Pd‐AAA). Hydroxyacrylates were used as unprecedented nucleophilic counterparts instead of widely used ketone substrates. This produced a very rare all‐carbon quaternary aldehyde. Chiral ligand (R,R)‐L3 was found to be optimal in this Pd‐AAA reaction and provided good to excellent yields (75–99 %) and enantioselectivities (75–94 %) with a range of analogs.