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

01 April 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


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.


Radical fluorination
N–F bond activation
charge transfer
Decarboxylative fluorination
Hydrogen atom transfer

Supplementary materials

Supporting Info
Experimental procedures and characterization of compounds


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