Manganese-Catalyzed Atroposelective Hydrophosphination of Alkynes To Access Vinylphosphine Atropisomers

Homogeneous manganese pincer complexes have emerged as earth-abundant and versatile catalysts, offering a benign alternative to precious-metal-based systems in various organic transformations via metal–ligand cooperation (MLC). While these catalysts have demonstrated significant promise in asymmetric hydrogenation and the synthesis of central-chiral phosphines, their application in the construction of axial chirality remains largely underdeveloped. Herein, we report a manganese-catalyzed atroposelective hydrophosphination of sterically hindered 1-alkynylindoles with phosphines. This method provides a direct and efficient route to synthesize challenging C–N axially chiral vinylphosphine atropisomers with high regio- and enantioselectivity. The density functional theory (DFT) calculations demonstrated that the enantioselectivity is governed by the cooperative effect of multiple noncovalent interactions.