Direct Access to InherentlyChiral Phosphines viaan Enantioselective Palladium-Catalyzed Hirao Reaction

Chiral phosphines are indispensable motifs in asymmetric catalysis and bioactive compounds, yet efficient catalytic approaches to structurally diverse and nonclassical chiral phosphine frameworks remain limited. Herein, we report the first Pd-catalyzed enantioselective Hirao-type C-P coupling of racemic pillar[5]arene-derived triflates with SPOs, enabling direct access to inherently chiral phosphines via a dynamic kinetic asymmetric transformation. This transformation exhibits broad substrate scope, tolerates both symmetrical and unsymmetrical phosphine reagents, and delivers products in moderate to good yields with high enantioselectivities and excellent configurational stability. Mechanistic investigations combined with density functional theory (DFT) calculations reveal that stereocontrol originates from catalyst-substrate recognition mediated by multiple noncovalent interactions within a confined chiral pocket. Notably, the resulting inherently chiral phosphines can be readily converted into trivalent ligands and applied in asymmetric catalytic reactions, and they further display pronounced chiroptical and circularly polarized luminescence properties. This work establishes a versatile strategy for constructing inherently chiral phosphines and expands their potential applications in asymmetric catalysis and chiral optoelectronic materials.