Hydrolysis of 2-cyanopyridine to picolinamide was accelerated 100-300-fold, as compared with spontaneous hydrolysis, in the presence of a complex formed from Cu(I1) ion and (S)-l-benzyl-2-[(ethylamino)methyl]pyrrolidine at 30 OC and pH 6-9.5 in H20. The rate enhancement was attributed to the intramolecular attack of coordinated hydroxide ion at the cyano group of the coordinated cyanopyridine. No picolinic acid was detected in the reaction mixture. But the copper(I1)-catalyzed 2-cyanopyridine hydrolysis in the presence of (S)-1 -benzyl-2-[((2-hydroxyethyl)amino)methyl]pyrrolidine produced, in addition to picolinamide, about 30-60% of picolinic acid. No hydrolysis of picolinamide to picolinic acid was observed under the experimental conditions. The formation of picolinamide and of picolinic acid followed different pathways, the latter being a typical consecutive two-stage type reaction with a buildup of an intermediate complex. The hydrolysis of 2-cyanopyridine to picolinic acid is considered to result from the initial nucleophilic attack of the coordinated hydroxyethyl group at the cyano group of the coordinated cyanopyridine with the formation of an intermediate coordinated imino ester, which is in turn slowly hydrolyzed further to picolinic acid.