Manganese‐Catalyzed Mono‐N‐Methylation of Aliphatic Primary Amines without the Requirement of External High‐Hydrogen Pressure

Abstract The synthesis of mono‐ N ‐methylated aliphatic primary amines has traditionally been challenging, requiring noble metal catalysts and high‐pressure H 2 for achieving satisfactory yields and selectivity. Herein, we developed an approach for the selective coupling of methanol and aliphatic primary amines, without high‐pressure hydrogen, using a manganese‐based catalyst. Remarkably, up to 98 % yields with broad substrate scope were achieved at low catalyst loadings. Notably, due to the weak base‐catalyzed alcoholysis of formamide intermediates, our novel protocol not only obviates the addition of high‐pressure H 2 but also prevents side secondary N ‐methylation, supported by control experiments and density functional theory calculations.