Glycine enolates: the effect of formation of iminium ions to simple ketones on alpha-amino carbon acidity and a comparison with pyridoxal iminium ions

Journal of the American Chemical Society
Juan CrugeirasJohn P Richard

Abstract

Equilibrium constants in D2O were determined by 1H NMR analyses for formation of imines/iminium ions from addition of glycine methyl ester to acetone and from addition of glycine to phenylglyoxylate. First-order rate constants, also determined by 1H NMR, are reported for deuterium exchange between solvent D2O and the alpha-amino carbon of glycine methyl ester and glycine in the presence of increasing concentrations of ketone and Brønsted bases. These rate and equilibrium data were used to calculate second-order rate constants for deprotonation by DO- and by Brønsted bases of the alpha-imino carbon of the ketone adducts. Formation of the iminium ion between acetone and glycine methyl ester and between phenylglyoxylate and glycine is estimated to cause 7 unit and 15 unit decreases, respectively, in the pKa's of 21 and 29 for deprotonation of the parent carbon acids. The effect of formation of iminium ions to phenylglyoxylate and to 5'-deoxypyridoxal (DPL) [Toth, K.; Richard, J. P. J. Am. Chem. Soc. 2007, 129, 3013-3021] on the carbon acidity of glycine is similar. However, DPL is a much better catalyst than phenylglyoxylate of deprotonation of glycine, because of the exceptionally large thermodynamic driving force for conversion ...Continue Reading

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Citations

Oct 1, 2009·Journal of the American Chemical Society·Wing-Yin Tsang, John P Richard
Dec 25, 2010·Biochimica Et Biophysica Acta·John P RichardAna Rios
Jul 31, 2009·Current Opinion in Chemical Biology·John P RichardAna Rios
Mar 13, 2015·Nature Communications·Anupam BandyopadhyayJianmin Gao
Aug 28, 2015·Chemistry : a European Journal·Anupam Bandyopadhyay, Jianmin Gao
Mar 27, 2010·Journal of the American Chemical Society·Junming HoMichelle L Coote
Apr 7, 2010·Organic Letters·Albert E FeltenZachary D Aron
Feb 10, 2009·Journal of Chemical Theory and Computation·Junming Ho, Michelle L Coote
May 15, 2021·Advanced Healthcare Materials·Muhammad RizwanMolly S Shoichet
Aug 16, 2018·Accounts of Chemical Research·Samantha Cambray, Jianmin Gao
Jul 12, 2018·Journal of the American Chemical Society·Wei WenQi-Xiang Guo
Sep 1, 2021·Nature Communications·Weiqi CaiBaoguo Zhao
Nov 4, 2021·Journal of the American Chemical Society·Robert J MayerJoseph Moran
Jun 15, 2011·Biochimica Et Biophysica Acta·Michael D Toney

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