Tailored Manganese-Catalyzed Enantioconvergent Hydrophosphination to Access Remote P , C -Stereogenic Phosphines

Achieving stereocontrol over two remote, flexible P- and C-stereocenters with a single catalyst remains a formidable challenge in the construction of chiral phosphines. We herein report a manganese-catalyzed enantioconvergent hydrophosphination of racemic allylic alcohols via a borrowing hydrogen (BH) strategy. This approach utilizes a single tailored Mn catalyst to orchestrate a cascade of dehydrogenation, enantioconvergent P-H addition, and asymmetric hydrogenation. This method provides direct access to P,C-stereogenic γ-hydroxy phosphines with excellent enantio- and diastereoselectivity, offering an atom-economical and sustainable route to diverse, high-value chiral phosphine libraries.