Pd-f-spiroPhos-Catalyzed Asymmetric Allylic Amination and Alkylation of (E)-1,3-Diarylallyl Acetates.

Highly enantioselective palladium-catalyzed allylic amination and alkylation of 1,3-diarylallyl acetates have been developed using a ferroceneyl spirocyclic diphosphine ligand, f-spiroPhos, for the synthesis of chiral allyl amines and 2-allyl malonates, achieving high yields and excellent enantioselectivities (up to 99.9% ee). Moreover, the method has also been successfully applied to the preparation of chiral γ,δ-unsaturated ketones in high yields with excellent enantioselectivities. Significantly, this methodology offers a straightforward route for the asymmetric synthesis of chiral allyl amines, 2-allyl malonates, and γ,δ-unsaturated ketones under mild conditions.