Manganese(I)-Catalyzed H–P Bond Activation via Metal–Ligand Cooperation
Juana M. Pérez, Roxana Postolache, Marta Castiñeira Reis, Esther G. Sinnema, Denisa Vargová, F. de Vries, Edwin Otten, Luo Ge, Syuzanna R. Harutyunyan
Abstract
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.
Topics & Concepts
ChemistryCatalysisLigand (biochemistry)ManganeseMetalStereochemistryCombinatorial chemistryReaction mechanismMedicinal chemistryOrganic chemistryReceptorBiochemistryAsymmetric Hydrogenation and CatalysisCatalytic C–H Functionalization MethodsOrganoboron and organosilicon chemistry