The kinetics of amination of dimethyl glutarate (DMG) and dimethyl 2,4-dimethylglutarate (DMDMG), considered to be small-molecule analogs of poly(methyl acrylate) (PMA), by reactions with ethanolamine (EA), n-hexylamine (HAN), benzylamine (BZA), and cyclohexanemethylamine (CN) have been studied by means of solution C-13 NMR. For the amines considered, it is found that under similar conditions the rate constant for the replacement of the first eater group (k(0)) of DMG is always larger than that for the replacement of the eater groups of PMA that have no reacted neighbors. This is in keeping with less steric hindrance. As was observed for the functionalization of PMA, K (defined as k(1)/k(0)) is sensitive to the reaction medium but not to the reaction temperature. Comparison of the values of K for the reactions of the analogs to those for the reactions of PMA reveals that the polymer chain plays an important part in determining the kinetic parameters. The value of K is also found to be dependent on the size and hydrophobicity of the amines. Although the rates of reaction of meso and racemic forms of DMDMG with ethanolamine are virtually the same, those with HAN and CN show substantial differences. A model of intramolecular assisting effects that involves the formation of an eight-membered ring is proposed and discussed.