The tautomerization of glycine via a triple proton transfer was investigated both in the gas phase and in aqueous solution using the B3LYP/6-31+G(d,p) level of theory. Fully optimized complexes of the neutral and zwitterion forms of glycine with 1,3-propanediol were used for the reactant and product forms, respectively. The hydroxyl groups in the diol are conveniently oriented for glycine tautomerization through a concerted triple proton transfer facilitated by a network of three hydrogen bonds: N-H…O-H…O-H…O=C. The activation energy for the zwitterion à neutral process increases in solution. Also, the diol-glycine complex favors the neutral over the zwitterion form in a vacuum, but the opposite is true in solution. For comparative purposes, the tautomerization of glycine via a three-proton transfer mediated by two molecules of water was also examined. The results are qualitatively similar, albeit with activation energies that are smaller to those found in the corresponding diol-mediated tautomerization.
KEYWORDS: Glycine; zwitterion, diol-mediated tautomerization; water-mediated tautomerization