Morpholine, piperidine and pyrrolidine enamines of 2-methylcyclohexanone react with ethyl azodicarboxylate to give, after hydrolysis, 2-methyl-6-(N,N′-dicarbethoxy)hydrazinocyclohexanone in 49%, 47% and 84%, yield, respectively. The same enamines by reaction with phenyl isocyanate and subsequent hydrolysis furnish 2-methyl-6-phenylcarbamylcyclohexanone in 51%, 42% and 88% yield, respectively. These results reflect the percentages of the less substituted isomeric enamines and are in good agreement with those determined by NMR spectroscopy, 1-N-Morpholino-, 1-N-piperidino- and 1-N-pyrrolidino-2-(N,N′-dicarbethoxy)hydrazinocyclohex-1-en by kinetically controlled acidic hydrolysis, lead to the 2,6-disubstituted cyclohexanone having trans configuration, as results from NMR analysis and equilibration into the more stable cis isomer. The stereochemistry of such a reaction is reported and discussed.