Manganese(I)-Catalyzed H–P Bond Activation via Metal–Ligand Cooperation

Here we report that chiral Mn­(I) complexes are capable of H–P bond activation. This activation mode enables a general method for the hydrophosphination of internal and terminal α,β-unsaturated nitriles. Metal−ligand cooperation, a strategy previously not considered for catalytic H–P bond activation, is at the base of the mechanistic action of the Mn­(I)-based catalyst. Our computational studies support a stepwise mechanism for the hydrophosphination and provide insight into the origin of the enantioselectivity.