Palladium-catalyzed asymmetric hydrophosphination of internal alkynes: Atroposelective access to phosphine-functionalized olefins

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

Automated summary

A palladium-catalyzed underexplored atroposelective hydrophosphination reaction has been successfully achieved, producing C-N axially chiral trisubstituted olefins through reaction with secondary phosphines. The method demonstrates excellent regioselectivity, (E)-selectivity, and enantioselectivity, and can be applied to both symmetrical and nonsymmetrical secondary phosphines.