Efficient N-methylation of primary amides using methanol under Mn(I)-catalysis

Herein, we report the use of methanol, a renewable, cost-effective, and easily handled reagent, for the highly selective N-methylation of amides under mild conditions. The reaction is catalyzed by a well-defined Mn-PNP pincer complex and proceeds via the borrowing hydrogen strategy (BHS). This method exhibits broad functional group tolerance and utilizes methanol as a methylating agent, demonstrating exceptional monoselectivity for amides, which enhances its practical appeal. Additionally, a series of control experiments were conducted to provide deeper mechanistic insights into the transformation.