A d-Camphor-Based Schiff Base as a Highly Efficient N,P Ligand for Enantioselective Palladium-Catalyzed Allylic Substitutions

New Schiff bases derived from chiral d‐camphor were determined to be effective phosphine ligands for the asymmetric palladium‐catalyzed allylic alkylation of activated methylene compounds, the allylic etherification of alcohols, and the allylic amination of primary amines or secondary amines, in which the corresponding products with various functional groups were achieved in good yields with excellent enantioselectivities (up to >99 % ee). Remarkably, the palladium catalyst derived from Schiff base L2 afforded the highest level of enantioselectivity reported to date for allylic substitution reactions, including allylic etherification and allylic amination, which revealed the privileged role of d‐camphor‐derived Schiff bases in palladium‐catalyzed allylic substitution reactions. d‐Camphor as a springboard: The palladium‐catalyzed asymmetric allylic alkylation of structurally diverse nucleophiles provides products in excellent yields with high enantioselectivities (up to >99 % ee) in the presence of a rigid d‐camphor‐derived Schiff base with nitrogen and phosphorus atoms.