Selective N‐Monomethylation of Anilines with Methanol Catalyzed by Commercial Pd/C as an Efficient and Reusable Catalyst

Abstract N ‐methylation of amines is one of the most important C−N bond‐forming reactions and is widely utilized for the synthesis of numerous agrochemicals, drugs, natural products, and dyes. In this paper, the N ‐monomethylation of aniline derivatives using Pd/C catalyst and methanol as the methylation reagent was investigated. The N ‐monomethylation of various anilines was achieved with high activity and selectivity under relatively mild reaction conditions, and the yield of N ‐monomethyl anilines was over 90 %. Notably, the commercial, readily available, and inexpensive heterogeneous catalyst, Pd/C, could be easily recovered and reused more than five times with only a slight decrease in activity; gram‐scale experiments were also successfully performed.