Palladium Catalyzed Asymmetric Hydrophosphination of Internal Alkynes: Access to Phosphine-Functionalized Axially Chiral Olefins

Abstract

Palladium-catalyzed unprecedented atroposelective hydrophosphination of sterically hindered internal alkynes with secondary phosphines has been realized, affording C-N axially chiral trisubstituted olefins (vinylphosphines) in excellent regioselectivity, (E)-selectivity, and enantioselectivity. The axial chirality was constructed via integration of hydrophosphination and dynamic kinetic transformation of the alkynes, with both symmetrical and nonsymmetrical secondary phosphines being applicable.