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dc.contributor.authorYu, Cihang
dc.contributor.authorKütt, Agnes
dc.contributor.authorRöschenthaler, Gerd-Volker
dc.contributor.authorLebl, Tomas
dc.contributor.authorCordes, David B.
dc.contributor.authorSlawin, Alexandra M. Z.
dc.contributor.authorBuehl, Michael
dc.contributor.authorO'Hagan, David
dc.identifier.citationYu , C , Kütt , A , Röschenthaler , G-V , Lebl , T , Cordes , D B , Slawin , A M Z , Buehl , M & O'Hagan , D 2020 , ' Janus face all- cis 1,2,4,5-tetrakis(trifluoromethyl)- and all- cis 1,2,3,4,5,6-hexakis(trifluoromethyl)- cyclohexanes ' , Angewandte Chemie International Edition , vol. 59 , no. 45 , pp. 19905-19909 .
dc.identifier.otherPURE: 269274158
dc.identifier.otherPURE UUID: b39e5a2e-7612-4c18-9963-dc8b3720bb9a
dc.identifier.otherRIS: urn:E304C0A09AD8144559065E07F8A97B2F
dc.identifier.otherORCID: /0000-0002-0269-3221/work/79917784
dc.identifier.otherORCID: /0000-0002-1095-7143/work/79917822
dc.identifier.otherORCID: /0000-0002-0510-5552/work/79917827
dc.identifier.otherORCID: /0000-0002-9527-6418/work/79917833
dc.identifier.otherORCID: /0000-0002-5366-9168/work/79917848
dc.identifier.otherScopus: 85090058738
dc.identifier.otherWOS: 000564434400001
dc.descriptionAuthors thank the Engineering and Physical Sciences Research Council (EPSRC) for funding and the Chinese Scholarship Council for a studentship (CY).en
dc.description.abstractWe report the synthesis of all‐cis 1,2,4,5‐tetrakis (trifluoromethyl)‐ and all‐cis 1,2,3,4,5,6‐hexakis (trifluoromethyl)‐ cyclohexanes by direct hydrogenation of precursor tetrakis‐ or hexakis‐ (trifluoromethyl)benzenes. The resultant cyclohexanes have a stereochemistry such that all the CF3 groups are on the same face of the cyclohexyl ring. All‐cis 1,2,3,4,5,6‐hexakis(trifluoromethyl)cyclohexane is the most sterically demanding of the all‐cis hexakis substituted cyclohexanes prepared to date, with a barrier (ΔG) to ring inversion calculated at 27 kcal mol−1. The X‐ray structure of all‐cis 1,2,3,4,5,6‐hexakis(trifluoromethyl)cyclohexane displays a flattened chair conformation and the electrostatic profile of this compound reveals a large diffuse negative density on the fluorine face and a focused positive density on the hydrogen face. The electropositive hydrogen face can co‐ordinate chloride (K≈103) and to a lesser extent fluoride and iodide ions. Dehydrofluorination promoted decomposition occurs with fluoride ion acting as a base.
dc.relation.ispartofAngewandte Chemie International Editionen
dc.rightsCopyright © 2020 The Authors. Published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution‐NonCommercial‐NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made.en
dc.subjectJanus faceen
dc.subjectTrifluoromethyl groupsen
dc.subjectAryl hydrogenationen
dc.subjectTriaxial orientationsen
dc.subjectQD Chemistryen
dc.titleJanus face all-cis 1,2,4,5-tetrakis(trifluoromethyl)- and all-cis 1,2,3,4,5,6-hexakis(trifluoromethyl)- cyclohexanesen
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.description.statusPeer revieweden

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