Regioselective control of the thiocarbonylation of terminal acetylenes with arylthiols catalyzed by Pd(II) and diphosphine ligands

Control of the regioselective thiocarbonylation of terminal acetylenes 1a-e with arylthiols 2a,b was successfully achieved by using Pd(OAc)(2) and 1,4-bis(diphenylphosphino)butane (dppb), or 1,3-bis(diphenylphosphino)propane (dppp), as catalysts. The formation of the thioesters 3 or 4 depends mainly on the type of ligand (dppp or dppb) and the solvent (THF or CH2Cl2) under CO/H+ or syngas mixture. (C) 2001 Elsevier Science Ltd. All rights reserved.