Enantiopure -Chiral Secondary Phosphines (P*HRR') from the Catalytic Asymmetric Hydrogenation of P═C Bonds.

We report the first bottleable enantiopure -chiral secondary phosphines from the rhodium-catalyzed asymmetric hydrogenation of phosphaalkenes. Catalytic asymmetric hydrogenation, a reaction of broad academic and industrial importance for C═C, N═C, and O═C bonds, has not previously been reported for the P═C bond. The hydrogenation of ArP═CR (Ar = Mes, -Xyl and TMOP; R = Ph, 4-CHF) affords four unprecedented -stereogenic secondary phosphines in 76%-90% isolated yields with 91%-97% enantiomeric excess (ee). These isolable -chiral secondary phosphines are configurationally stable indefinitely in the solid state and show only modest loss in ee when kept in solution for over a month at room temperature.