α-Aryl malonate and α-aryl cyano acetate moieties are found in the structures of many bioactive compounds. They are also key intermediates for the synthesis of many compounds such as isoflavonoids. In this work, we synthesized these compounds, with different patterns of substitution, starting with the palladium-catalyzed reaction of o-alkoxybromoarenes with dimethyl malonate or ethyl cyanoacetate. Under the conditions applied, moderate to good yields of arylmalonate monoesters, phenylacetic esters or acids, and benzylnitrile derivatives were obtained.