The selective mono-N-methylation of anilines derivatives was achieved under mild conditions using inexpensive methanol as Cl source. Under hydrogen borrowing conditions, using a tridentate (PNP)-P-3 manganese pre-catalyst (5 mol%), a catalytic amount of base (20 mol%), for 24 h at 120 degrees C, a large variety of anilines derivatives was methylated in good to excellent yield. Mechanistic investigations allowed us to isolate and characterize by X-ray diffraction studies a de-aromatized manganese intermediate. (C) 2017 Elsevier Inc. All rights reserved.