Asymmetric Hydrophosphination of Heterobicyclic Alkenes: Facile Access to Phosphine Ligands for Asymmetric Catalysis

Abstract

Asymmetric hydrophosphination is the most atomically economical and straightforward approach to the construction of chiral organophosphorus compounds. Good stereoselectivities have been achieved in asymmetric hydrophosphination of an electron-deficient C═C double bond, but substrates involving nonpolar C═C bonds remain difficult and are rarely tackled. Herein, we report asymmetric hydrophosphination of a non-electronically activated double bond with a remarkably high degree of stereocontrol. This strategy offered an expedient and broadly applicable platform to prepare tertiary phosphines in high yields (up to 99% yield) and enantioselectivities (up to 99% ee). Particularly noteworthy is that these tertiary phosphine products were then successfully employed as phosphine ligands in enantioselective metal-catalyzed transformations with a high level of asymmetric induction.