Cobalt‐based catalysts can replace the homologous group‐9 rhodium‐based ones. Herein, we used density functional theory (DFT) calculations to predict the synthesis of 2,3‐dihydropyridines using α,β‐unsaturated oxime pivalates and alkenes catalysed by [Cp*CoOAc]+ instead of [Cp*RhOAc]+. The catalytic cycle involves reversible acetate‐assisted metalation‐deprotonation, migratory insertion of alkenes, and reductive elimination/N‐O cleavage. The migratory insertion of alkenes was determined to be the rate‐determining step, and the reaction is irreversible due to the strongly exergonic reductive elimination/NO cleavage. When using the CF3‐substituted Cp*Co(III) catalyst, the apparent activation energy indicates that the title reaction can proceed at higher temperatures. Electron‐withdrawing substituent groups on Cp* facilitate the reaction. In contrast, substituting phenyl with the electron‐deficient p‐CF3‐phenyl at the 2‐position of α,β‐unsaturated oxime pivalate hinders the reaction, and so does the use of polarized alkenes with electron‐withdrawing substituent groups

The reaction of Cp*(Cl)Hf(2,3-dimethylbutadiene) with isonitriles is theoretically investigated, and detailed elementary reactions and the substitution effects are examined.

Reaction of Cp*(Cl)Ti(2,3-dimethylbutadiene) with isonitriles is studied using DFT, detailed elementary reaction steps and N-substitution effects of isonitrile are examined.