The chelating ligand bis[2-(diphenylphosphino)phenyl] ether (DPEphos), in combination with palladium acetate, forms a highly active catalyst system for the coupling of anilines with aryl bromides. The bisphosphine is easily prepared in large quantity and at low cost by a known procedure. The catalyst system is effective in coupling reactions involving a variety of substrates, including electron-poor anilines or electron-rich aryl bromides. In addition, it tolerates a high degree of steric congestion at both the aniline and the aryl bromide. (C) 1998 Elsevier Science Ltd. All rights reserved.