Cobalt Catalyzed N-Methylation of Amides using Methanol

N-Methylation of amide with methanol is reported in the presence of an in-situ generated cobalt catalyst. With this simple protocol, various amides were methylated in up to 99% yield. Notably, the involvement of active cobalt (I) hydride in this methylation process was revealed by control experiments. Deuterium labelling studies were carried out using methanol-d(4,) taking benzamide and the possible intermediate N-(hydroxymethyl)benzamide to understand this transformation. Additionally, DFT calculations for the amide-formaldehyde coupling were performed to elucidate the influence of catalyst in this step.