Mechanistic Insights Into the Cobalt‐Catalyzed Carbonylative Coupling of Amines and Alkenes by Density Functional Theory Calculations

Mechanistic understanding of the cobalt‐catalyzed carbonylative coupling of amines and alkenes for amide synthesis was achieved by density functional theory (DFT) calculations. The results indicate that the regioselective insertion of the alkene into the Co–H bond of the active HCo(CO) 3 species is governed by distortion the latter moiety in the TS. After formation of the acylcobalt species, the amide bond is formed easily by nucleophilic attack of the amine. The final amide product is formed by further steps of N‐H deprotonation and catalyst regeneration. A manifested high energy was predicted for alcoholysis of the acylcobalt intermediate, which correlates to the failed production of esters via a similiar transformation.