Selective electrochemical fluorination of organic molecules and macromolecules in ionic liquids

Abstract

This article provides an outline of recent studies on selective electrochemical fluorination in ionic liquid fluoride salts toward green sustainable chemistry. First, a brief historical background of electrochemical fluorination in organic solvents is provided, and some particular problems and unique solvent effects associated with this technique are briefly mentioned. Second, recent progress in selective fluorination and fluorodesulfurization of organic molecules and macromolecules in ionic liquids using direct and indirect electrolysis with recyclable mediators is reviewed.

Elektrifizierung der organischen Synthese

“…[13] Methods for the selective chemical fluorination of organic substrates suffer from the hazardous character of most fluorinating reagents,a swella st heir significant costs. [14] Electrochemical perfluorination of organic substrates in anhydrous HF at Ni anodes,k nown as the commercially used Simons process,w as already developed in 1949, [15] and later enhanced by using molten KF·2 HF and carbon anodes. [16] Thef irst report on selective partial fluorination dates back to 1970, and this process was further developed mainly by Fuchigami and co-workers.Most of the advances accomplished in this area have recently been summarized.…”

Cyclohexane-Based Liquid-Biphasic Systems for Organic Electrochemistry

“…In other words, the required amount of the supporting electrolyte for the reaction was reduced significantly through this system. In addition to hex-1-ene (21), several olefin nucleophiles (23)(24)(25) were then introduced to this system (Fig. 15).…”

“…In organic electrochemistry, electrodes have been utilized as solid-phase redox reagents to trigger either one-or two-electron transfers that afford various functional group transforma-tions and a wide variety of carbon-carbon bond formations in a controlled manner [20][21][22][23][24][25]. In particular, there is good chemistry between electrochemical approaches and cyclic compounds to produce complex ring systems in one step.…”

Sodium Salts Dissolution in an Aprotic Solvent by Coordination of Poly(ethylene glycol) for Effective Anodic Reactions of Organic Compounds

“…10 Although MF is insoluble in MeCN, the addition of PEG markedly promoted the solubility and dissociation of MF by coordination of PEG to metal cation. 11 Since Et 3 N·nHF and Et 4 NF·nHF (n = 35) have been mainly used for anodic fluorination so far, 9 our new electrolytic system, namely MF-PEG/ MeCN offered an alternative efficient method for anodic fluorination of organic compounds.…”

“…Modern strategies of electroorganic synthesis 2 focus on reducing the amount of supporting electrolyte by using solid polymer elecrolyte (SPE), 3,4 microflow reactors, 5,6 polymersupported base, 7,8 and ionic lquids. 8,9 These approaches well contributed to the development of green electrode process; however, each reaction systems is somewhat specialized.…”