What question did this study set out to answer?

The aim is to understand the mechanism of cobalt-catalyzed carbonylative coupling for amide synthesis using DFT calculations.

April 1, 2026

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

Key Points

The aim is to understand the mechanism of cobalt-catalyzed carbonylative coupling for amide synthesis using DFT calculations.
Conducted density functional theory (DFT) calculations to model reaction pathways.
Analyzed regioselective insertion of alkenes into cobalt–hydride bonds.
Investigated the formation and transformation of acylcobalt species.
Identified distortion of the HCo(CO)3 species as key to regioselectivity.
Confirmed that amide bond formation occurs efficiently via nucleophilic attack by amines.
Predicted high energy for alcoholysis of the acylcobalt intermediate, indicating challenges in ester formation.

Abstract

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.

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

Key Points

Abstract

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