Recent Development in Synthesis of N‐Methylamines with Amines and Methanol

Abstract The N‐methylation reaction of amines with methanol via the borrowing‐hydrogen strategy is an important method for the construction of C−N bonds. Compared with other C1 sources, such as toxic formaldehyde or expensive formic acid, methanol is more suitable for N‐methylation reactions due to its eco‐friendliness and low price. Using this strategy, various types N‐methylated products, including biological and pharmaceutical molecules have been prepared. Here, we present a thorough survey of decades of articles showing current developments in N‐methylation reactions with methanol. We discuss homogenous, heterogenous and light‐driven catalytic systems for both N‐methylation and N,N‐dimethylation reactions. This review presents the shortcomings of current developments and provides future development progress in N‐methylation reactions with methanol.