Unique solvent effects on selective electrochemical fluorination of organic compounds

Abstract

Recent studies on solvent effects on electrochemical partial fluorination are reviewed. At first, the historical background and some problems of electrochemical fluorination in organic solvents like acetonitrile (MeCN) are briefly mentioned. Ethereal solvents like dimethoxyethane (DME) and a mixture of DME and MeCN were found to improve both the yield and current efficiency for electrochemical fluorination since these solvent systems effectively suppress anode passivation and overoxidation of fluorinated products once formed during the electrolysis. It was also found that DME stabilizes radical cationic intermediates of 4-arylthio-1,3-dioxolan-2-ones and 3-phenylthiophthalide leading to α-fluorination while dichloromethane (CH 2Cl 2) destabilizes them leading to fluorodesulfurization. On the other hand, imidazolium ionic liquids and liquid fluoride salts like Et 4NF·4HF and Et 3N·5HF exhibited similar effects to CH 2Cl 2. Selective fluorination of hardly oxidizable phthalide was also achieved using a combination of two kinds of ionic liquids (imidazolium triflate and liquid fluoride salts).