Commercially available [(PPh 3 ) 2 NiCl 2 ] was found to be an efficient catalyst for the mono- N -alkylation of (hetero)aromatic amines, employing alcohols to deliver diverse secondary amines, including the drug intermediates chloropyramine ( 5b ) and mepyramine ( 5c ), in excellent yields (up to 97%) via the borrowing hydrogen strategy. This method shows a superior activity (TON up to 10000) with a broad substrate scope at a low catalyst loading of 1 mol % and a short reaction time. Further, this strategy is also successful in accessing various quinoline derivatives following the acceptorless dehydrogenation pathway.