Tailored Manganese-Catalyzed Enantioconvergent Hydrophosphination to Access Remote <i>P</i> , <i>C</i> -Stereogenic Phosphines

Achieving stereocontrol over two remote, flexible <i>P</i>- and <i>C</i>-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 <i>P,C</i>-stereogenic <i>γ</i>-hydroxy phosphines with excellent enantio- and diastereoselectivity, offering an atom-economical and sustainable route to diverse, high-value chiral phosphine libraries.