The electrophilic fluorination of enol esters using SelectFluor : a polar two-electron process

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Wood, Susanna H. and Etridge, Stephen and Kennedy, Alan R. and Percy, Jonathan M. and Nelson, David J. (2019) The electrophilic fluorination of enol esters using SelectFluor : a polar two-electron process. Chemistry - A European Journal, 25 (21). pp. 5574-5585. ISSN 1521-3765 (https://doi.org/10.1002/chem.201900029)

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Abstract

The reaction of enol esters with SelectFluor is facile and leads to the corresponding α-fluoroketones under mild conditions and, as a result, this route is commonly employed for the synthesis of medicinally important compounds such as fluorinated steroids. However, despite the use of this methodology in synthesis, the mechanism of this reaction and the influence of structure on reactivity are unclear. We present a rigorous mechanistic study of the fluorination of these substrates, informed primarily by detailed and robust kinetic experiments. The results of this study implicate a polar two-electron process via an oxygen-stabilised carbenium species, rather than a single-electron process involving radical intermediates. The structure/reactivity relationships revealed here will assist synthetic chemists in deploying this type of methodology in the syntheses of α-fluoroketones

ORCID iDs

Wood, Susanna H. ORCID logoORCID: https://orcid.org/0000-0002-4253-7979, Etridge, Stephen, Kennedy, Alan R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, Percy, Jonathan M. ORCID logoORCID: https://orcid.org/0000-0001-8636-2704 and Nelson, David J. ORCID logoORCID: https://orcid.org/0000-0002-9461-5182;
  • Item type:Article
    ID code:66951
    Dates:
    Date
    Event
    11 April 2019
    Published
    6 February 2019
    Published Online
    6 February 2019
    Accepted
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:13 Feb 2019 18:19
    Last modified:18 Dec 2024 01:23
    URI:https://strathprints.strath.ac.uk/id/eprint/66951
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