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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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.
Yu , 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 . https://doi.org/10.1002/anie.202008662
Angewandte Chemie International Edition
Copyright © 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.
DescriptionAuthors thank the Engineering and Physical Sciences Research Council (EPSRC) for funding and the Chinese Scholarship Council for a studentship (CY).
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