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dc.contributor.authorPiscelli, Bruno
dc.contributor.authorSanders, William
dc.contributor.authorYu, Cihang
dc.contributor.authorAl-Maharik, Nawaf
dc.contributor.authorLebl, Tomas
dc.contributor.authorCormanich, Rodrigo
dc.contributor.authorO'Hagan, David
dc.date.accessioned2020-08-19T08:30:02Z
dc.date.available2020-08-19T08:30:02Z
dc.date.issued2020-09-16
dc.identifier.citationPiscelli , B , Sanders , W , Yu , C , Al-Maharik , N , Lebl , T , Cormanich , R & O'Hagan , D 2020 , ' Fluorine induced pseudo -anomeric effects in methoxycyclohexanes through electrostatic 1,3-diaxial interactions ' , Chemistry - A European Journal , vol. 26 , no. 52 , pp. 11989-11994 . https://doi.org/10.1002/chem.202003058en
dc.identifier.issn0947-6539
dc.identifier.otherPURE: 268893409
dc.identifier.otherPURE UUID: b602d73a-34c4-4359-9e4b-670af59e02f8
dc.identifier.otherORCID: /0000-0002-0269-3221/work/79226717
dc.identifier.otherORCID: /0000-0002-0510-5552/work/79226750
dc.identifier.otherScopus: 85089465763
dc.identifier.otherWOS: 000560363700001
dc.identifier.urihttp://hdl.handle.net/10023/20484
dc.descriptionAuthors thank FAPESP, CONFAP and The UK Academies for a São Paulo International Research Collaboration (FAPESP #2019/05028-7). FAPESP is also gratefully acknowledge for an undergraduate fellowship to BAP (#2019/03855-3), and a Young Research Award to RAC (#2018/03910-1). The Chinese Scholarship Council (CSC) is thanked for a Studentship (CY). Finally CENAPAD-SP, CESUP and SDumont are acknowledged for computational resources used in theory calculations.en
dc.description.abstractWe report counter‐intuitive axial preferences in non‐stereochemically biased, selectively fluorinated methoxycyclohexanes. These pseudo‐anomeric effects are apparent when electronegative CF2 groups are placed at the C‐2, C‐4 and C‐6 positions of the cyclohexane ring to render the C‐3/5 axial hydrogen atoms electropositive. The electrostatic interaction between these axial hydrogen atoms and the ‐OMe oxygen is stabilising. The effect is explored using high‐level ab initio and DFT calculations in the framework of NBO, QTAIM and NCI analysis across a range of derivatives, and experimentally (19F{1H}‐NMR at −80 °C) for some illustrative examples. The effect is significant in energy terms for a weak interaction, and illustrates a new stereoelectronic aspect attributed to selective fluorine substitution in organic chemistry.
dc.format.extent7
dc.language.isoeng
dc.relation.ispartofChemistry - A European Journalen
dc.rightsCopyright © 2020 The Authors. Published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.en
dc.subjectOrganofluorineen
dc.subjectAnomeric effecten
dc.subjectConformational analysisen
dc.subjectStereoelectronic effectsen
dc.subjectComputational chemistryen
dc.subjectQD Chemistryen
dc.subjectT-NDASen
dc.subject.lccQDen
dc.titleFluorine induced pseudo-anomeric effects in methoxycyclohexanes through electrostatic 1,3-diaxial interactionsen
dc.typeJournal articleen
dc.description.versionPublisher PDFen
dc.contributor.institutionUniversity of St Andrews.School of Chemistryen
dc.contributor.institutionUniversity of St Andrews.EaSTCHEMen
dc.contributor.institutionUniversity of St Andrews.Biomedical Sciences Research Complexen
dc.identifier.doihttps://doi.org/10.1002/chem.202003058
dc.description.statusPeer revieweden
dc.date.embargoedUntil2020-08-18


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