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.