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The Electrophilic Fluorination of Enol Esters Using SelectFluor: A Polar Two‐Electron Process
Author(s) -
Wood Susanna H.,
Etridge Stephen,
Kennedy Alan R.,
Percy Jonathan M.,
Nelson David J.
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201900029
Subject(s) - selectfluor , electrophile , reactivity (psychology) , enol , chemistry , polar , computational chemistry , electrophilic fluorination , combinatorial chemistry , organic chemistry , photochemistry , catalysis , physics , medicine , alternative medicine , pathology , astronomy
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. A rigorous mechanistic study of the fluorination of these substrates is presented, 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.