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Janus face all-cis 1,2,4,5-tetrakis(trifluoromethyl)- and all-cis 1,2,3,4,5,6-hexakis(trifluoromethyl)- cyclohexanes

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Author(s)

Cihang Yu, Agnes Kütt, Gerd-Volker Röschenthaler, Tomas Lebl, David B. Cordes, Alexandra M. Z. Slawin, Michael Buehl, David O'Hagan

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Abstract

We 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.
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Original languageEnglish
Number of pages6
JournalAngewandte Chemie International Edition
VolumeEarly View
Early online date1 Sep 2020
DOIs
Publication statusE-pub ahead of print - 1 Sep 2020

    Research areas

  • Janus face, Cyclohexanes, Trifluoromethyl groups, Aryl hydrogenation, Triaxial orientations

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