The effect of the structure of the achiral primary amine additive on the enantioselective heterogeneous catalytic hydrogenation of (E)-2-methyl-2-butenoic acid over cinchonidine modified Pd/Al2O3 was studied. It was found that a variety of amines increase the enantioselectivity, which was always accompanied by decrease in the initial rate of the hydrogenations. Based on these results, the participation of the amine additive in the formation of the intermediate complex responsible for enantioselection was suggested. A decrease in the reaction temperature resulted in further increase in the optical purity of the product up to 67%, the highest value reported in the hydrogenation of unsaturated aliphatic acids in this heterogeneous catalytic system so far.