Disentangling the Conformational Space and Structural Preferences of Tetrahydrofurfuryl Alcohol Using Rotational Spectroscopy and Computational Chemistry

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dc.contributor.authorDias de Paiva Silva, Weslley Guilherme
dc.contributor.authorvan Wijngaarden, Jennifer
dc.date.accessioned2024-06-07T20:56:21Z
dc.date.available2024-06-07T20:56:21Z
dc.date.issued2024-04-18
dc.description© 2024 The Authors. ChemPhysChem published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution Non-Commercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.
dc.description.abstractThe influence of the hydroxymethyl (CH2OH) group on the tetrahydrofuran (THF) ring structure was investigated by disentangling the gas phase conformational landscape of the sugar analogue tetrahydrofurfuryl alcohol (THFA). By combining rotational spectroscopy (6–20 GHz) and quantum chemical calculations, transitions corresponding to two stable conformers of THFA and their 13C isotopologues were observed and assigned in the rotational spectrum. The positions of the C atoms were precisely determined to unambiguously distinguish between nearly isoenergetic pairs of conformers that differ in their ring configurations: envelope (E) versus twist (T). The rotational spectrum confirms that the E ring geometry is favoured when the CH2OH fragment lies gauche (−) to the THF backbone (OCCO ~−60°) whereas the T form is more stable for the gauche (+) alignment of the substituent (OCCO ~+60°). The observed spectral intensities suggest that conformational relaxation of the THF geometry (E↔T) to the more stable form readily occurs within the pairs of g− and g+ conformers which is consistent with the low barriers (1.5–1.7 kJ mol−1) for conversion determined via transition state calculations. Insights into the intramolecular hydrogen bonding and other weak interactions stabilizing the lowest energy structures of THFA were derived and rationalized using non-covalent interaction analyses.
dc.description.sponsorshipThis research is funded by the Natural Sciences and Engineering Research Council of Canada (NSERC) through the Discovery Grant program (JvW) and the high-performance computing facility (GREX) provided by the University of Manitoba and Digital Research Alliance of Canada. W. G. D. P. S. also acknowledges support from a UMGF during his time at the University of Manitoba.
dc.identifier.citationSilva, W. G. D. P.; van Wijngaarden, J. Disentangling the Conformational Space and Structural Preferences of Tetrahydrofurfuryl Alcohol Using Rotational Spectroscopy and Computational Chemistry. ChemPhysChem 2024, e202400298. DOI: 10.1002/cphc.202400298
dc.identifier.issn1439-7641
dc.identifier.urihttps://doi.org/10.1002/cphc.202400298
dc.identifier.urihttps://hdl.handle.net/10315/42073
dc.language.isoen
dc.rightsAttribution-NonCommercial 4.0 Internationalen
dc.rights.urihttp://creativecommons.org/licenses/by-nc/4.0/
dc.subjectConformational analysis
dc.subjectRotational spectroscopy
dc.subjectComputational chemistry
dc.subjectHydrogen bonds
dc.subjectNoncovalent interactions
dc.titleDisentangling the Conformational Space and Structural Preferences of Tetrahydrofurfuryl Alcohol Using Rotational Spectroscopy and Computational Chemistry
dc.typeArticle

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