Mechanistic Study on Decarbonylative Phosphorylation of Aryl Amides by Nickel Catalysis

The phosphorylation of amide represents an unprecedented environmentally friendly and easily achievable method to constitute C–P bonds in organic synthesis. In this study, the mechanisms for the nickel-catalyzed direct decarbonylative phosphorylation of amides recently reported by Szostak's team were systematically studied with density functional theory calculations. The reaction mainly undergoes four steps: oxidative addition (rate-determining step), phosphorylation, decarbonylation, and reductive elimination. The structures of the substrate and Na2CO3 were found to be critical for the reaction efficiency. Substrates bearing electron-withdrawing groups like carbonyl groups near the amide bond facilitate the reaction by weakening the C–N bond, and Na2CO3 can not only neutralize the H atom in the phosphate ligand as an alkali but also activate the Ni–N bond through the coordination bond with the adjacent carbonyl of the amide group.