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Benzylic Fluorination Induced by a Charge-Transfer Complex with a Solvent-Dependent Selectivity Switch

Amiera Madani, Lucia Anghileri, Matthias Heydenreich, Heiko M. Möller, Bartholomäus Pieber

2022Organic Letters23 citationsDOIOpen Access PDF

Abstract

We present a divergent strategy for the fluorination of phenylacetic acid derivatives that is induced by a charge-transfer complex between Selectfluor and 4-(dimethylamino)pyridine. A comprehensive investigation of the conditions revealed a critical role of the solvent on the reaction outcome. In the presence of water, decarboxylative fluorination through a single-electron oxidation is dominant. Non-aqueous conditions result in the clean formation of α-fluoro-α-arylcarboxylic acids.

Topics & Concepts

ChemistrySelectfluorSelectivitySolventPhenylacetic acidPyridineAqueous solutionCharge (physics)Electron transferSolvent effectsPhotochemistryOrganic chemistryCombinatorial chemistryComputational chemistryCatalysisQuantum mechanicsPhysicsFluorine in Organic ChemistryRadical Photochemical ReactionsCyclopropane Reaction Mechanisms