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An Unexpected and Significantly Lower Hydrogen-Bond-Donating Capacity of Fluorohydrins Compared to Nonfluorinated Alcohols†

Authors

  • Dr. Jérôme Graton,

    Corresponding author
    1. CEISAM UMR CNRS 6230, Faculté des Sciences et des Techniques, Université de Nantes, 2, rue de la Houssinière – BP 92208, 44322 NANTES Cedex 3 (France)
    • CEISAM UMR CNRS 6230, Faculté des Sciences et des Techniques, Université de Nantes, 2, rue de la Houssinière – BP 92208, 44322 NANTES Cedex 3 (France)
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  • Zhong Wang,

    1. Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ (UK)
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  • Anne-Marie Brossard,

    1. CEISAM UMR CNRS 6230, Faculté des Sciences et des Techniques, Université de Nantes, 2, rue de la Houssinière – BP 92208, 44322 NANTES Cedex 3 (France)
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  • Daniela Gonçalves Monteiro,

    1. Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ (UK)
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  • Prof. Dr. Jean-Yves Le Questel,

    1. CEISAM UMR CNRS 6230, Faculté des Sciences et des Techniques, Université de Nantes, 2, rue de la Houssinière – BP 92208, 44322 NANTES Cedex 3 (France)
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  • Dr. Bruno Linclau

    Corresponding author
    1. Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ (UK)
    • Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ (UK)
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  • †

    D.G.M. thanks Chemistry, University of Southampton for support. We thank for access to the HPC resources of [CCRT/CINES/IDRIS] under the allocation c2012085117 made by GENCI (Grand Equipement National de Calcul Intensif) and the CCIPL (Centre de Calcul Intensif des Pays de la Loire) for grants of computer time.

Abstract

original image

Rewriting the rules as fluorination does not always increase hydrogen-bond acidity: while the strongly electron-withdrawing fluorine significantly enhances alcohol H-bond acidity in anti-vicinal fluorohydrins, an intramolecular F⋅⋅⋅HO interaction overrules completely the inductive effect. This leads to an overall decrease in alcohol H-bond acidity, compared to the corresponding nonfluorinated alcohol.

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Article Information

DOI

10.1002/anie.201202059

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Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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Keywords

  • computational chemistry;
  • conformation analysis;
  • fluorine;
  • fluorohydrins;
  • hydrogen bonding

Publication History

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Funded by

  • Funded Access
  • Chemistry, University of Southampton
  • GENCI (Grand Equipement National de Calcul Intensif)

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