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A study of intramolecular hydrogen bonding in levoglucosan derivatives

A study of intramolecular hydrogen bonding in levoglucosan derivatives
A study of intramolecular hydrogen bonding in levoglucosan derivatives
Organofluorine is a weak hydrogen-bond (HB) acceptor. Bernet et al. have demonstrated its capability to perturb OH···O intramolecular hydrogen bonds (IMHBs), using conformationally rigid carbohydrate scaffolds including levoglucosan derivatives. These investigations are supplemented here by experimental and theoretical studies involving six new levoglucosan derivatives, and complement the findings of Bernet et al. However, it is shown that conformational analysis is instrumental in interpreting the experimental data, due to the occurrence of non-intramolecular hydrogen-bonded populations which, although minor, cannot be neglected and appears surprisingly significant. The DFT conformational analysis, together with the computation of NMR parameters (coupling constants and chemical shifts) and wavefunction analyses (AIM, NBO), provides a full picture. Thus, for all compounds, the most stabilized structures show the OH groups in a conformation allowing IMHB with O5 and O6, when possible. Furthermore, the combined approach points out the occurrence of various IMHBs and the effect of the chemical modulations on their features. Thus, two-center or three-center IMHB interactions are observed in these compounds, depending on the presence or absence of additional HB acceptors, such as methoxy or fluorine.
hydrogen bond, intramolecular interaction, NMR coupling constants, quantum calculations, fluorination, levoglucosan
Quiquempoix, Lucas
29de2855-0a16-43a2-8987-dfc823f61458
Bogdan, Elena
bd2b4c26-9ae0-42eb-8397-3c8d95f48060
Wells, Neil
86312185-007b-495b-86da-4e2e5b9b8025
Le Questel, Jean-Yves
38aea4ae-64a3-43b7-8049-ea2f351459f2
Graton, Jérôme
12432694-552e-4a40-9935-9ff7c77fbf07
Linclau, Bruno
19b9cacd-b8e8-4c65-af36-6352cade84ba
Quiquempoix, Lucas
29de2855-0a16-43a2-8987-dfc823f61458
Bogdan, Elena
bd2b4c26-9ae0-42eb-8397-3c8d95f48060
Wells, Neil
86312185-007b-495b-86da-4e2e5b9b8025
Le Questel, Jean-Yves
38aea4ae-64a3-43b7-8049-ea2f351459f2
Graton, Jérôme
12432694-552e-4a40-9935-9ff7c77fbf07
Linclau, Bruno
19b9cacd-b8e8-4c65-af36-6352cade84ba

Quiquempoix, Lucas, Bogdan, Elena, Wells, Neil, Le Questel, Jean-Yves, Graton, Jérôme and Linclau, Bruno (2017) A study of intramolecular hydrogen bonding in levoglucosan derivatives. Molecules, 22 (4). (doi:10.3390/molecules22040518).

Record type: Article

Abstract

Organofluorine is a weak hydrogen-bond (HB) acceptor. Bernet et al. have demonstrated its capability to perturb OH···O intramolecular hydrogen bonds (IMHBs), using conformationally rigid carbohydrate scaffolds including levoglucosan derivatives. These investigations are supplemented here by experimental and theoretical studies involving six new levoglucosan derivatives, and complement the findings of Bernet et al. However, it is shown that conformational analysis is instrumental in interpreting the experimental data, due to the occurrence of non-intramolecular hydrogen-bonded populations which, although minor, cannot be neglected and appears surprisingly significant. The DFT conformational analysis, together with the computation of NMR parameters (coupling constants and chemical shifts) and wavefunction analyses (AIM, NBO), provides a full picture. Thus, for all compounds, the most stabilized structures show the OH groups in a conformation allowing IMHB with O5 and O6, when possible. Furthermore, the combined approach points out the occurrence of various IMHBs and the effect of the chemical modulations on their features. Thus, two-center or three-center IMHB interactions are observed in these compounds, depending on the presence or absence of additional HB acceptors, such as methoxy or fluorine.

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2017 molecules - Version of Record
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Accepted/In Press date: 21 March 2017
e-pub ahead of print date: 24 March 2017
Published date: 24 March 2017
Keywords: hydrogen bond, intramolecular interaction, NMR coupling constants, quantum calculations, fluorination, levoglucosan
Organisations: Characterisation and Analytics, Chemistry, Organic Chemistry: SCF

Identifiers

Local EPrints ID: 406861
URI: https://eprints.soton.ac.uk/id/eprint/406861
PURE UUID: e0a2d9fb-d47b-4f6e-a85f-59f707997e02
ORCID for Neil Wells: ORCID iD orcid.org/0000-0002-4607-5791
ORCID for Bruno Linclau: ORCID iD orcid.org/0000-0001-8762-0170

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Date deposited: 25 Mar 2017 02:01
Last modified: 10 Sep 2019 00:50

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Contributors

Author: Lucas Quiquempoix
Author: Elena Bogdan
Author: Neil Wells ORCID iD
Author: Jean-Yves Le Questel
Author: Jérôme Graton
Author: Bruno Linclau ORCID iD

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