A series of chelating phosphines as ligands of palladium complexes was used for the catalytic reaction of bromobenzene with ethyl cyanoacetate anion and it was found that dppe-Pd catalytic system has the highest activity to obtain ethyl phenylcyanoacetate among all ligands. The effects of molar ratio of dppe to catalyst, solvent, temperature and bases on the reaction were discussed. The substituted bromobenzene reacted with ethyl cyanoacetate anion under the appropriate reaction conditions to give the cross-coupling products in considerable yield. (C) 2002 Elsevier Science B.V. All rights reserved.