Direct Synthesis of Phosphine‐Phosphite Ligand and Its Implication in Asymmetric Hydrogenation of Functionalized Olefins

Phosphine–phosphite (P‐OP) ligands constitute a privileged class of chiral ligands in asymmetric catalysis owing to their modular structures and tunable steric and electronic properties. Herein, we report a direct, one‐pot, synthesis of a new flexible P‐OP ligand (L) derived from BINOL‐PCl and its in situ complexation with rhodium (Rh) for catalytic evaluation. The resulting Rh/L system efficiently hydrogenates a diverse library of 19 functionalized olefins under mild conditions, delivering moderate to excellent enantioselectivities, with ee values reaching up to 99%. Several of the hydrogenated products correspond to valuable chiral building blocks relevant to pharmaceutical synthesis, underscoring the practical utility of flexible P‐OP ligand architectures in asymmetric hydrogenation.