Desymmetrization of Achiral Heterobicyclic Alkenes through Catalytic Asymmetric Hydrophosphination.

Asymmetric addition of diarylphosphines to oxa- and azabicyclic alkenes proceeded in the presence of a chiral phosphapalladacycle catalyst and a mild acid at room temperature to give exclusively the enantioenriched addition products in excellent yields and good selectivities. Three new chiral carbon centers were generated stereoselectively by the catalytic hydrophosphination reaction.