Apparent Electrophilic Fluorination of 1,3‐Dicarbonyl Compounds Using Nucleophilic Fluoride Mediated by PhI(OAc)₂

Abstract

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.

Fluorohydration of alkynes via I(I)/I(III) catalysis

“…Moreover, elegant studies by Hara and co-workers have demonstrated that α-fluoroketones could be prepared by exposing silyl enol ethers to stoichiometric p -ToIIF 2 , in the presence of BF 3 ·OEt 2 and NEt 3 /HF 1:2 [ 38 ]. A report by Kitamura and co-workers in which the direct fluorination of acetophenone derivatives was achieved using iodosylarenes and commercially available NEt 3 /HF 1:5 to generate the ArIF 2 species in situ is also highly pertinent [ 39 – 40 ] ( Fig. 1 ).…”

Metal-Free Catalytic Asymmetric Fluorination of Keto Esters Using a Combination of Hydrogen Fluoride (HF) and Oxidant: Experiment and Computation

“…Regarding the development of transition-metal-free processes, elegant fluorination protocols were designed using hypervalent iodine species . In the initial fluorination studies, stoichiometric loadings of hypervalent iodine species were applied in versatile reactions with a wide range of nucleophiles. , Catalytic protocols using an aryl iodide, a fluoride, and various oxidants were also published using m -chloroperbenzoic acid ( m CPBA) or an electric current. − …”

Conformational preferences of α-fluoroketones may influence their reactivity

“…α-Halogenated ketones are widely used electrophiles in organic synthesis, being highly reactive in both nucleophilic addition to the carbonyl group and in S N 2 nucleophilic displacements [ 1 ]. Our research group has recently been exploring the synthesis and reactivity of α-fluorinated ketones [ 2 – 4 ] and here their reactivity relative to other halogenated ketones is compared.…”