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(Reference retrieved automatically from Web of Science through information on FAPESP grant and its corresponding number as mentioned in the publication by the authors.)

Does intramolecular hydrogen bond play a key role in the stereochemistry of alpha- and beta-D-glucose?

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Silla, Josue M. [1] ; Cormanich, Rodrigo A. [2] ; Rittner, Roberto [2] ; Freitas, Matheus P. [1]
Total Authors: 4
[1] Univ Fed Lavras, Dept Chem, BR-37200000 Lavras, MG - Brazil
[2] Univ Estadual Campinas, Inst Chem, BR-13083970 Campinas, SP - Brazil
Total Affiliations: 2
Document type: Journal article
Source: Carbohydrate Research; v. 396, p. 9-13, SEP 19 2014.
Web of Science Citations: 23

Four alpha- and three beta-isomers of the D-glucose were optimized in gas phase using ab initio (MP2) and DFT (omega B97X-D) methods, both using the aug-cc-pVDZ basis set. While earlier works suggest that the orientation of the hydroxyl groups is due to intramolecular hydrogen bonds (H-bonds), the present study reveals that most H-bonds forming five-membered rings are either weak or even do not exist. The quantum theory of atoms in molecules (QTAIM) analysis showed only a few cases of H-bond in D-glucose, particularly for those H-bonds forming six-membered rings, while the non-covalent interactions (NCI) analysis indicated that most intramolecular H-bonds are not strong enough to justify the counter-clockwise arrangement of the OH center dot center dot center dot O chains. Natural bond orbital analysis supported the findings obtained from QTAIM and NCI analyses and indicated that the anomeric effect for D-glucose in the gas phase is governed by a balance of steric, electrostatic, and hyperconjugative interactions. (C) 2014 Elsevier Ltd. All rights reserved. (AU)

FAPESP's process: 12/03933-5 - Conformational equilibria and intramolecular interactions for a series of amino-acids: theoretical and experimental approaches
Grantee:Roberto Rittner Neto
Support type: Regular Research Grants
FAPESP's process: 11/01170-1 - Physicochemical studies of organic compounds: long range inractions and conformational analysis of organofluorine compounds.
Grantee:Rodrigo Antonio Cormanich
Support type: Scholarships in Brazil - Doctorate