(1.2-Dibromomoethyl)arenes, obtained from the bromination of styrene derivatives were regioselectivley dehydrobrominated to alpha-arylvinyl bromides in very good yields (82-94%). The vinyl bromides generated in Situ underwent palladium-catalyzed carbonylation furnishing 2-arylacrylic esters, which are precursors for non-steroidal anti-inflammatory drugs. The best catalytic system is composed of PdCl2(PPh3)(2) (0.5-2mol%), PPh3 as phosphine ligand and iPrEtN as base. The carbonylation reaction can be carried out under mild conditions (10 atm of CO, 100 degrees C, 3.5 h) affording the esters in very good yields (88-95%). Moreover, we have developed a one-pot deydrobromination/carbonylation procedure. (c) 2005 Elsevier B.V. All rights reserved.