Electrolytic partial fluorination of organic compounds. 1. Regioselective anodic monofluorination of organosulfur compounds

Fuchigami, Toshio; Shimojo, M.; Konno, Akinori; Nakagawa, K.

doi:10.1021/jo00312a006

Cited by 114 publications

(47 citation statements)

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“…Electrochemical selective fluorination has been established in our group by using ionic liquid hydrogen fluoride (HF) salts like Et 3 NnHF and Et 4 NF-nHF (n = 3-5) as a supporting electrolyte and a fluorine source. [1] Ionic liquids have unique physical and chemical properties and have recently received much attention. For example, ionic liquids are employed in organic synthesis as green reaction media instead of volatile organic compounds (VOC).…”

Section: Introductionmentioning

confidence: 99%

Prins Cyclization in Ionic Liquid Hydrogen Fluoride Salts: Facile and Highly Efficient Synthesis of 4‐Fluorinated Tetrahydropyrans, Thiacyclohexanes, and Piperidines

Kishi

Inagi

2008

Eur J Org Chem

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Prins cyclization of homoallylic alcohols with various aldehydes was investigated in ionic liquid hydrogen fluoride (HF) salts, which played roles as a reaction medium, a catalyst, and a fluorine source. The reaction afforded the corresponding 4‐fluorinated tetrahydropyrans in excellent yields with a high stereoselectivity (cis form exclusively). When benzaldehydes having a strongly electron‐donating group at the para position were used, the stereoselectivity was lost in this system. In order to apply this method to the synthesis of other 4‐fluorinated heterocyclic compounds, we also carried out thia‐Prins and aza‐Prins cyclization in HF salt and successfully obtained 4‐fluorinated thiacyclohexanes and piperidines, respectively.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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Section: Introductionmentioning

confidence: 99%

Prins Cyclization in Ionic Liquid Hydrogen Fluoride Salts: Facile and Highly Efficient Synthesis of 4‐Fluorinated Tetrahydropyrans, Thiacyclohexanes, and Piperidines

Kishi

Inagi

2008

Eur J Org Chem

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“…3HF/MeCN. 180,181 Since anode passivation takes place during the anodic fluorination, pulse electrolysis is necessary to avoid the anode passivation. Anodic difluorination of 1 was unsuccessful in the same electrolyte solution, while anodic fluorination of α-monofluorinated acetate (2) gave the α,α-difluorinated product (3) in moderate yield after passing a large excess amount of electricity (Scheme 3): 182 Momota and co-workers 183 developed a new series of liquid fluoride salts, R 4 NF.nHF (R = Me, Et, and n-Pr, n > 3.5), that are useful in partial fluorination.…”

Section: Organic Synthesis In Ionic Liquidsmentioning

confidence: 99%

Electrochemical routes for industrial synthesis

Sequeira¹,

Santos²

2009

J. Braz. Chem. Soc.

112

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Esta revisão examina as razões que justificam um interesse crescente da indústria química pelos processos eletrolíticos. Reveem-se as indústrias químicas, nas quais compostos orgânicos e inorgânicos são processados e descrevem-se os avanços tecnológicos mais relevantes. Inicialmente, abordam-se processos bem estabelecidos, como as indústrias cloroalcalinas de produção de alumínio, p-aminofenol, adiponitrila, etileno glicol, antraquinona, produtos perfluorados, ácido glioxílico e L-cisteína. Face à grande quantidade de informação disponível, o assunto é tratado com base científica, mas de modo bastante simplificado. Posteriormente, descrevem-se processos orgânicos e inorgânicos emergentes, nomeadamente processos eletroquímicos mediados e síntese em líquidos iónicos. Estabelecem-se paralelos entre síntese química e síntese eletroquímica. Estimula-se o interesse nos processos de eletrossíntese, particularmente em líquidos iónicos, não desmerecendo a importância das vias puramente químicas de síntese orgânica e inorgânica.This review examines the reasons for increasing interest towards electrolyses by the chemical industry, reviews the electrochemical industries as most of them now exist, and provides a status report on the key technological advances which are occurring to meet present and future needs. Classical industries like those of chloroalkali, aluminium, p-aminophenol, adiponitrile, ethylene glycol, anthraquinone, perfluorinated products, glyoxylic acid and L-cysteine are initially covered. Considering the large amount of available publications in these topics of electrochemical engineering, the covered relevant information is treated at a scientific level, although in a simplified way. Then the paper deals with emerging inorganic and organic processes, e.g. electrosynthesis in ionic liquids and mediated electrochemical processes, and finishes by assessing what the future development trend might be given the electrochemical and non electrochemical competing influences. With this approach it is hoped to stimulate the interest of chemical engineers and scientists non-specialised in electrochemical routes, and to review some cutting edge research, particularly as far as electrosynthesis in ionic liquids is concerned.

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“…Fuchigami's group and Laurent's group have independently achieved anodic afluorination of a-phenylthioacetate (1) in Et 3 N Á3HF/MeCN [12,13]. Since anode passivation takes place during the anodic fluorination, pulse electrolysis is necessary to avoid the anode passivation.…”

Section: Selective Anodic Fluorinationmentioning

confidence: 99%