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

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.