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 alpha,beta-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.

Automated summary

Chiral Mn(I) complexes have been shown to activate H-P bonds, providing a general method for the hydrophosphination of internal and terminal alpha,beta-unsaturated nitriles. Metal-ligand cooperation, a previously unconsidered strategy for catalytic H-P bond activation, plays a key role in the mechanistic action of the Mn(I)-based catalyst. Computational studies support a stepwise mechanism for the hydrophosphination reaction and offer insights into the origin of enantioselectivity.