Electrolytic Partial Fluorination of Organic Compounds. 22.<sup>1</sup> Highly Regioselective Anodic Monofluorination of Oxindole and 3-Oxo-1,2,3,4-tetrahydroisoquinoline Derivatives: Effects of Supporting Fluoride Salts and Anode Materials

Hou, Yankun; Higashiya, Seiichiro

doi:10.1021/jo971173i

Cited by 41 publications

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“…Electrochemical fluorination of oxindole and cyclic phosphonate was achieved similarly. 46,47 It was also found that the selectivity of fluorination was strongly influenced by ionic liquid fluoride salts (Scheme 10). 48 Since Et 3 N-3HF contains the free base Et 3 N, the difluorinated product, once formed, was dehydrofluorinated to the monofluoro product.…”

Section: Selective Electrochemical Fluorination In Organic Solventsmentioning

confidence: 99%

Selective electrochemical fluorination of organic molecules and macromolecules in ionic liquids

2011

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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.

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Section: Selective Electrochemical Fluorination In Organic Solventsmentioning

confidence: 99%

Selective electrochemical fluorination of organic molecules and macromolecules in ionic liquids

2011

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“…Platinum has been typically employed for electrochemical fluorination as an anode material. However, carbon plate and carbon sheet anodes are also effective in the electrochemical fluorination of 1-phenyl-3-(phenylthio)oxindole in Et 4 NF–4HF/MeCN, and a glassy carbon (GC) anode is much better than a Pt anode in some cases, as exemplified in Scheme . However, such anode material effects are case-by-case.…”

Section: Parameters For Selectivity and Efficiency In Electrochemical...mentioning

confidence: 99%

Recent Advances in Electrochemical Systems for Selective Fluorination of Organic Compounds

2020

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Metrics & MoreArticle Recommendations CONSPECTUS: Organofluorine compounds are key materials applied in daily life because of their versatile utility as functional materials, pharmaceuticals, and agrochemicals. Development of the selective fluorination of organic molecules under safe conditions is therefore one of the most important subjects in modern synthetic organofluorine chemistry. Thus, various electrophilic fluorination reagents such as XeF 2 , (PhSO 2 ) 2 NF (NFSI), Et 2 NSF 3 (DAST), (MeOCH 2 CH 2 ) 2 NSF 3 (Deoxofluor), 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo-[2.2.2]octane bis-(tetrafluoroborate) (Selectfluor), N-fluoropyridinium salts, and 4-tertbutyl-2,6-dimethylphenylsulfur trifluoride (Fluolead) have been developed for chemical fluorination to date and the development of new fluorinating reagents is still ongoing.Electrochemical synthesis has recently attracted much attention from the perspective of green sustainable chemistry because no hazardous reagents are required and scale-up is generally easy. Although electrochemical perfluorination of organic compounds using a nickel anode in anhydrous HF has been well-established to manufacture perfluoro-functional materials, electrochemical partial fluorination (selective electrochemical fluorination) has been underdeveloped due to the low nucleophilicity of fluoride ions and anode passivation, which interferes with electrolysis. Selective electrochemical fluorination can be commonly achieved in aprotic solvents containing fluoride ions to provide mostly mono-and difluorinated products. Electrolysis is conducted at constant potentials slightly higher than the first oxidation potential of a substrate. Constant current electrolysis is also effective for selective fluorination in many cases. Choice of the combination of a supporting fluoride salt and an electrolytic solvent is most important to accomplish efficient selective fluorination.In this Account, we focus on our recent work on the electrochemical mono-and difluorination of various organic compounds and their synthetic application. We first briefly explain our research background of electrochemical fluorination. Main factors such as the effects of fluoride salts as supporting electrolytes, electrolytic solvents, and anode materials on the selectivity and efficiency of fluorination are discussed. Next, effects of PEG oligomer additives enhancing the nucleophilicity of fluoride ions and organic solventfree systems using poly(HF) salt ionic liquids as well as recyclable mediatory systems for electrochemical fluorination are described.The desulfurizative monofluorination of xanthate and gem-difluorination of benzothioate and dithioacetals are briefly mentioned.Regioselective anodic fluorination of various heterocyclic compounds having a phenylthio group as electroauxiliary and heterocycles containing sulfur and other heteroatoms are also described. In addition, a boryl group is shown to be a good leaving group for anodic fluorination. Moreover, electrochemically α,α-difluorinated phenylsulfides and ph...

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“…Highly regioselective, anodic monofluorination of oxindole and 3-oxo-1,2,3,4-tetrahydroisoquinoline can be achieved by using Et 4 NF-mHF (m = 3, 4) (Scheme 40) [67].…”

Section: Fluorination Of Heterocyclic Ringsmentioning

confidence: 99%

Electrochemical Fluorination for Preparation of Alkyl Fluorides

Inagi

2017

Fluorination

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Electrolytic Partial Fluorination of Organic Compounds. 22.¹ Highly Regioselective Anodic Monofluorination of Oxindole and 3-Oxo-1,2,3,4-tetrahydroisoquinoline Derivatives: Effects of Supporting Fluoride Salts and Anode Materials

Cited by 41 publications

References 27 publications

Selective electrochemical fluorination of organic molecules and macromolecules in ionic liquids

Selective electrochemical fluorination of organic molecules and macromolecules in ionic liquids

Recent Advances in Electrochemical Systems for Selective Fluorination of Organic Compounds

Electrochemical Fluorination for Preparation of Alkyl Fluorides

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Electrolytic Partial Fluorination of Organic Compounds. 22.1 Highly Regioselective Anodic Monofluorination of Oxindole and 3-Oxo-1,2,3,4-tetrahydroisoquinoline Derivatives: Effects of Supporting Fluoride Salts and Anode Materials

Cited by 41 publications

References 27 publications

Selective electrochemical fluorination of organic molecules and macromolecules in ionic liquids

Selective electrochemical fluorination of organic molecules and macromolecules in ionic liquids

Recent Advances in Electrochemical Systems for Selective Fluorination of Organic Compounds

Electrochemical Fluorination for Preparation of Alkyl Fluorides

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Electrolytic Partial Fluorination of Organic Compounds. 22.¹ Highly Regioselective Anodic Monofluorination of Oxindole and 3-Oxo-1,2,3,4-tetrahydroisoquinoline Derivatives: Effects of Supporting Fluoride Salts and Anode Materials