Palladium/copper-catalyzed Sonogashira cross-coupling reaction of aryl halides with a variety of terminal alkynes under amine-free conditions in dimethylformamide (DMF) at 80 degrees C gave internal arylated alkynes using PdCl2(MeCN)2 with phosphine-free hydrazone 2a as a ligand and CuI as the cocatalyst in good yields. We also found PdCl2/hydrazone ligand 1d in PhMe at 80 degrees C was a phosphine-free efficient catalyst system for a Hiyama cross-coupling reaction of aryl bromides with aryl(trialkoxy)silanes in good yields.
