Mechanisms of chemoselectivity for acyl and decarbonylative Suzuki–Miyaura coupling of N-acetyl amide with arylboronic acid catalyzed by Pd and Ni catalysts: Insights from DFT calculations

Abstract

The reaction mechanisms for palladium-catalyzed acyl and nickel-catalyzed biaryl Suzuki-Miyaura cross-coupling of N-acetyl-amide with arylboronic acid have been investigated via density functional theory (DFT) calculations. The calculations demonstrated that two catalysts Ni/PCy3 and Pd/PCy3 lead to different catalytic cycles. In the case of Ni/PCy3 catalyst, the favorable catalytic cycle to give product biaryl contains four steps, oxidative addition, transmetallation, decarbonylation, and reductive elimination. In the case of Pd/PCy3 catalyst, the favorable catalytic cycle to yield product ketone proceeds by three steps, oxidative addition, transmetallation and reductive elimination. Present calculations are consistent with the experimental results and could provide new insights into the development of Pd and Ni catalysts for highly selective reactions.