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Gas‐phase acidity of D ‐glucose. A density functional theory study
Author(s) -
Salpin JeanYves,
Tortajada Jeanine
Publication year - 2004
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/jms.671
Subject(s) - chemistry , deprotonation , anomer , gas phase , basis set , computational chemistry , anomeric effect , ring (chemistry) , phase (matter) , stereochemistry , density functional theory , medicinal chemistry , organic chemistry , ion
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 α‐ and β‐anomers may easily occur under slightly energetic conditions. B3LYP/6–311+G(2df,2p) calculations led to the an absolute gas‐phase acidity of Δ acid G o 298 (α‐ 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. Copyright © 2004 John Wiley & Sons, Ltd.