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A formal catalytic cycle for the metal ion-catalyzed hydrolyses of acrylamide and acrylate esters is described. While various transition metal ions show little acceleration of hydrolysis reactions in free water, bringing them into proximity with esters and amides can yield increased hydrolysis rates. Such proximity effects can be brought about by covalent addition of donor atoms near the functional group. However, the simple conjugate adducts of butylmethylamine to methyl acrylate and to acrylamide did not demonstrate metal ion-catalyzed hydrolysis. Conjugate addition of a chelating amine, IV-benzyl-lV'^V'-dimethylethylenediamine, yields adducts demonstrating significant (up to 1.5 x 104-fold) hydrolysis catalysis by Cu(II) at pH 7.5 and room temperature. A model compound to test for improvement of this effect by conformational locking demonstrated no rate increase. A model compound designed to test for enhanced acceleration by two adjacent metal ions similarly showed no rate advantage as compared to the parent conjugate adduct. The conjugate reversion reaction of 3-((2-(dimethylamino)ethyl)benzylamino)propionic acid demonstrated a bellshaped pH-rate profile with maximum rate at pH 3.

Conjugate addition of N-benzyl-N',N'-dimethylethylenediamine to acrylamide affords a chelating amide in which the amide carbonyl can coordinate to the bound metal only via a six-membered chelate; this compound demonstrates copper(i1)-catalysed amide hydrolysis, in which each metal acts on at least five equivalents of substrate.