Jump to main content
Jump to site search

Issue 35, 2018
Previous Article Next Article

Enantioselective fluorination of homoallylic alcohols enabled by the tuning of non-covalent interactions

Author affiliations

Abstract

The study of the enantioselective fluorination of homoallylic alcohols via chiral anion phase transfer (CAPT) catalysis using an in situ generated directing group is described. Multivariate correlation analysis, including designer π-interaction derived parameters, revealed key structural features affecting the selectivity at the transition state (TS). Interpretation of the parameters found in the model equation highlights the key differences as well as similarities for the reaction of homoallylic and allylic substrates. A similar T-shaped π-interaction was found to occur between the substrate and the catalyst. The tuning of this crucial interaction by identification of the best combination of phosphoric acid catalyst and boronic acid directing group allowed for the development of a methodology to access γ-fluoroalkenols in typically high enantioselectivities (up to 96% ee).

Graphical abstract: Enantioselective fluorination of homoallylic alcohols enabled by the tuning of non-covalent interactions

Back to tab navigation

Supplementary files

Publication details

The article was received on 20 May 2018, accepted on 25 Jul 2018 and first published on 03 Aug 2018


Article type: Edge Article
DOI: 10.1039/C8SC02223B
Chem. Sci., 2018,9, 7153-7158
  • Open access: Creative Commons BY-NC license
    All publication charges for this article have been paid for by the Royal Society of Chemistry

  •   Request permissions

    Enantioselective fluorination of homoallylic alcohols enabled by the tuning of non-covalent interactions

    J. A. S. Coelho, A. Matsumoto, M. Orlandi, M. J. Hilton, M. S. Sigman and F. D. Toste, Chem. Sci., 2018, 9, 7153
    DOI: 10.1039/C8SC02223B

    This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material and it is not used for commercial purposes.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements