Chiral amines are privileged chiral building blocks with extensive applications in pharmaceuticals, advanced materials, and asymmetric catalysis owing to their unique structural features and functional diversity. Although palladium-catalyzed asymmetric allylic C–H amination offers an efficient strategy for constructing these motifs, the simultaneous challenges of coordinating sterically hindered internal alkenes and suppressing catalyst deactivation by Lewis basic amines have severely limited the development of asymmetric oxidative amination systems. In this study, we disclose a novel ester, an unmodified native functional group-directed strategy that enables the palladium-catalyzed asymmetric oxidative allylic amination of internal α,β-unsaturated esters with basic amines. This protocol yields a diverse array of non-natural γ-amino acid derivatives with excellent yields and high enantioselectivity (93% to >99% e.e.). Comprehensive mechanistic investigations, incorporating controlled experiments and density functional theory calculations, elucidate the intricate reaction pathway. The synthetic utility is further demonstrated through various product derivatizations and the streamlined synthesis of bioactive compounds. This work establishes a general platform for accessing enantioenriched nitrogen-containing architectures from readily available alkenes and amines.
