Apparent electrophilic fluorination of 1,3-dicarbonyl compounds using nucleophilic fluoride mediated by PhI(OAc)₂

The apparent electrophilic fluorination of 1,3-dicarbonyl compounds using Et₃N·3HF as a nucleophilic fluoride source is reported. This reaction requires PhI(OAc)₂ as oxidant and can be conducted safely in standard laboratory glassware. Alternative selectivity compared to Selectfluor was observed in some cases. This approach may reduce our reliance on difficult-to-handle fluorine gas and expensive electrophilic fluorinating agents derived from elemental fluorine. Mechanistic analysis related to the active fluorinating species and fluoride/acetate exchange is presented. The apparent electrophilic fluorination of 1,3-dicarbonyl compounds using Et₃N·3HF mediated by the in-situ formation of PhIF₂ from PhI(OAc)₂ is reported. This can be performed safely in standard laboratory glassware, and this approach may reduce our reliance on difficult-to-handle fluorine gas and expensive electrophilic fluorinating agents derived from elemental fluorine.