Palladium‐Catalyzed Methylation of Nitroarenes with Methanol

A procedure for the synthesis of N ‐methyl‐arylamines directly from nitroarenes using methanol as green methylating agent was developed. The key to success is the use of a specific catalyst system consisting of palladium acetate and the ligand 1‐[2,6‐bis(isopropyl)phenyl]‐2‐[tert‐butyl(2‐pyridinyl)phosphino]‐1 H ‐Imidazole ( L1 ). The generality of this protocol is demonstrated in the synthesis of more than 20 N ‐methyl‐arylamines under comparably mild conditions. Combining this novel methodology with subsequent coupling processes using the same catalyst allows for efficient diversification of aromatic nitro compounds to a broad variety of amines including drug molecules.