Isoquinolines, benzoisoquinolines, thieno[3,2-c]pyridines and fused heteroaryl[2,3-c] pyridines, with a wide variety of substituents at different positions of the aromatic or heteroaromatic rings, have been synthesized by Ru-catalyzed oxidative coupling of a broad range of benzylamines or heterocycles with internal alkynes. All benzylamines and heterocycles have unprotected primary amines as efficient directing groups.