Benzylic fluorination induced by N–F bond activation of Selectfluor® with a solvent-dependent selectivity switch

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

doi:10.26434/chemrxiv-2022-mstv5

Organic Chemistry

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Benzylic fluorination induced by N–F bond activation of Selectfluor® with a solvent-dependent selectivity switch

Working Paper

Amiera Madani Max-Planck-Institute of Colloids and Interfaces & Freie Universität Berlin ,
Lucia Anghileri Max-Planck-Institute of Colloids and Interfaces & Freie Universität Berlin ,
Matthias Heydenreich University of Potsdam ,
Heiko M. Möller University of Potsdam ,
Bartholomäus Pieber Max-Planck-Institute of Colloids and Interfaces

Abstract

We present a divergent radical strategy for the fluorination of phenylacetic acid derivatives through N–F bond activation of Selectfluor® with 4-(dimethylamino)pyridine. Comprehensive reaction investigation revealed the critical role of reaction media on selectivity. In 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 through hydrogen atom transfer.