Enantioselective hydrogenation of (Z)-beta-dehydroamino acids on a cinchonidine-modified Pd/Al2O3 catalyst was explored. Comparative studies by using (Z)-beta-dehydroamino acids and esters identified that the carboxylic group in dehydroamino acids was essentially important to get enantioselectivities (33% for aryl substituted and 46% for alkyl substituted beta-dehydroamino acids). This result extended the range of enantioselective hydrogenation of alpha,beta-unsaturated carboxylic acids on chirally modified Pd catalysts and offered a new approach to synthesize optically active beta-amino acids. (C) 2013 Elsevier B.V. All rights reserved.