C-H bond functionalization of aromatic heterocycles with chelating dicarbene palladium(II) and platinum(II) complexes

Chelating dicarbene complexes of palladium(II) and platinum(II) catalyse at room temperature with 1% catalyst loading the reaction of ethyl phenylpropiolate with aromatic heterocycles to yield synthetically useful intermediates for fine chemicals without the need to use prefunctionalized substrates. The reaction outcome was found to be strongly dependent on the nature of the anionic ligands at the metal complex. Addition of silver salts to replace halide ligands with more weakly coordinating anions improves the reaction yield and changes the product distributions: heterocycle-alkyne 2 : 1 adducts are obtained together with the usual hydroarylation products, which potentially broadens the scope of the reaction. The nature of the employed heterocycle, in particular its steric characteristics, is also found to strongly influence the outcome of the reaction. Copyright (C) 2009 John Wiley & Sons, Ltd.