Esterification, transesterification and hydrogenation reactions of polyunsaturated compounds catalyzed by a recyclable polymer supported palladium catalyst

Aliphatic and aromatic carboxylic acids were converted into their corresponding esters using a polymer supported palladium(II) β-ketoesterate complex under hydrogen atmosphere in the presence of catalytic bromobenzene in alcohols. This method was also applicable to the transesterification of esters. Good to excellent yields were obtained for different aliphatic or aromatic starting materials. The esterification (or transesterification) was promoted by the in situ generation of HBr from bromobenzene, which provided a mild acidic reaction environment. Pd(II) centers were converted into polymer stabilized metal nanoparticles (the true active species) under reaction conditions. The palladium catalyst exhibited a remarkable activity and was reusable for eight consecutive cycles. The present system was also tested for the preparation of partially hydrogenated fatty acid methyl esters, starting from a mixture composed by highly polyunsaturated esters and free carboxylic acids, taken as a model acidic feedstock for biodiesel upgrading.