The electrophilic fluorination of enol esters using SelectFluor : a polar two-electron process
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: https://orcid.org/0000-0002-4253-7979, Etridge, Stephen, Kennedy, Alan R. ORCID: https://orcid.org/0000-0003-3652-6015, Percy, Jonathan M. ORCID: https://orcid.org/0000-0001-8636-2704 and Nelson, David J. ORCID: https://orcid.org/0000-0002-9461-5182;-
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Item type: Article ID code: 66951 Dates: DateEvent11 April 2019Published6 February 2019Published Online6 February 2019AcceptedSubjects: Science > Chemistry Department: Faculty of Science > Pure and Applied Chemistry Depositing user: Pure Administrator Date deposited: 13 Feb 2019 18:19 Last modified: 12 Oct 2024 00:26 URI: https://strathprints.strath.ac.uk/id/eprint/66951