Gas-phase acidity of D-glucose. A density functional theory study

Journal of Mass Spectrometry : JMS
Jean-Yves Salpin, Jeanine Tortajada

Abstract

The gas-phase acidity of D-glucopyranose was studied by means of B3LYP calculations combined with 6-31G(d,p) or 6-31+G(d,p) standard basis sets. For each anomer, deprotonation of the various primary and secondary hydroxyl groups was considered. As in solution, the anomeric hydroxyl is found to be the most acidic for both anomers, but only when the 6-31+G(d,p) basis set is used for geometry optimization. Deprotonation of the anomeric hydroxyl induces an important C(1)--O endocyclic bond elongation and subsequently promotes an energetically favored ring-opening process as attested by the very small calculated activation barriers. The results also suggest that interconversion between the various deprotonated alpha- and beta-anomers may easily occur under slightly energetic conditions. B3LYP/6-311+G(2df,2p) calculations led to the an absolute gas-phase acidity of deltaacidGo(298)(alpha-D-glucose) = 1398 kJ mol(-1). This estimate matches well the only experimental value available to date. Finally, this study again confirms that the use of diffuse functions on heavy atoms is necessary to describe anionic systems properly and to achieve good relative and absolute gas-phase acidities.

Citations

Aug 15, 2013·Journal of the American Society for Mass Spectrometry·Yixuan ZhangJohn S Klassen
Feb 17, 2005·Rapid Communications in Mass Spectrometry : RCM·Raymond E March, Christopher J Stadey
Sep 30, 2008·Chemistry : a European Journal·Robert D RichardsonDarren J Dixon
Jun 15, 2007·Journal of Mass Spectrometry : JMS·Ahlam El FirdoussiJean-Yves Salpin
Jun 5, 2007·Rapid Communications in Mass Spectrometry : RCM·Seetharaman Vaidyanathan, Royston Goodacre
Apr 15, 2016·Journal of Molecular Modeling·Gang YangLijun Zhou
May 28, 2013·The Journal of Physical Chemistry. a·Shuting FengGiannis Mpourmpakis
Apr 23, 2017·Magnetic Resonance in Chemistry : MRC·John S Lomas, Laurent Joubert
May 27, 2017·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Estefania Rossich MolinaRiccardo Spezia
Aug 3, 2017·The Journal of Physical Chemistry Letters·Shinichi EnamiA J Colussi

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