Manganese‐Catalyzed Selective Hydration of Nitriles to Primary Amides: Experimental and Theoretical Studies

ABSTRACT Herein, we present the selective hydration of nitriles to primary amides using a manganese complex based on a bidentate phosphine ligand DPPP (1,3‐bis(diphenylphosphaneyl)propane) under mild conditions. The described process offers good to exceptional isolated yields of the corresponding primary amides, demonstrating substrate versatility with promising functional group tolerance. The substrates include a diverse array of (hetero)aromatic and aliphatic nitriles. We have also carried out a comprehensive computational study on base metal‐catalyzed nitrile hydration to understand the catalytic reaction mechanism along with similar catalysts reported earlier. Our findings reveal that structural and electronic perturbations, along with solvation, seem to affect catalytic activity and the energy profile of the overall catalytic cycle.