Thiofluorination of Carbon–Carbon Multiple Bonds Using Electrochemically Generated ArS(ArSSAr)+BF4−

Fujie, Shunsuke; Matsumoto, Kouichi; Suga, Seiji; Yoshida, Junichi

doi:10.1246/cl.2009.1186

Cited by 37 publications

(20 citation statements)

References 32 publications

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“…21, 22 For example, thiofluorinated compound 14 was obtained exclusively in the reaction with 1-octene at 0 • C, whereas the reaction at -78 • C gave diarylthio-substituted compound 7 as shown in Scheme 6. 23 In this case, a fluoride ion, which is derived from the anionic part of supporting electrolyte (BF 4 -), attacked the episulfonium ion intermediate 10 as a nucleophile before a quenching reagent was added to the reaction mixture (Scheme 5). The reactions of ArS(ArSSAr) + BF 4…”

Section: Methodsmentioning

confidence: 99%

Organic reactions mediated by electrochemically generated ArS+

2011

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Low-temperature electrochemical oxidation of ArSSAr was carried out to generate a pool of "ArS(+)". Spectroscopic studies ((1)H NMR and CSI-MS) of the resulting solution revealed the accumulation of ArS(ArSSAr)(+). The resulting "ArS(+)" pool reacted with alkenes and alkynes to give diarylthio-substituted products. The "ArS(+)" pool rapidly reacted with thioacetals to give the corresponding alkoxycarbenium ion pools, which reacted with various carbon nucleophiles (indirect cation pool method). The reaction of the alkoxycarbenium ion pools with stilbene derivatives in the presence of ArSSAr gave thiochroman derivatives. In addition to such stoichiometric reactions, a catalytic amount of "ArS(+)" serves as an initiator and a chain carrier of some cationic chain reactions involving intramolecular carbon-carbon bond formation. In situ generation of "ArS(+)" by electrochemical oxidation of ArSSAr with a catalytic amount of electricity in the presence of a substrate is also effective for such cationic chain reactions.

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Section: Methodsmentioning

confidence: 99%

Organic reactions mediated by electrochemically generated ArS+

2011

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“…Similarly, the anodic oxidation of aryl disulfides at low temperatures allowed the accumulation of highly electrophilic ArS + equivalent which could form episulfonium intermediates upon reaction with olefins or alkynes (Figure B, left). − The thiirane could be opened directly with hard nucleophiles such as fluorides or alkoxides. Nevertheless, due to the presence of disulfides in solution, treatment of the episulfonium with soft nucleophiles led to the formation of vicinal disulfides instead.…”

Section: Anodic Oxidationmentioning

confidence: 99%

Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance

2017

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“…Reactions at higher temperatures such as 0 °C without quenching lead to the addition of an ArS group and F derived from BF 4 − onto carbon−carbon multiple bonds (Scheme 74). 160 This transformation serves as a useful method for introducing fluorine atoms into organic molecules.…”

Section: R 2 (R′o)s + Ionsmentioning

confidence: 99%

Electrogenerated Cationic Reactive Intermediates: The Pool Method and Further Advances

2017

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Electrochemistry serves as a powerful method for generating reactive intermediates, such as organic cations. In general, there are two ways to use reactive intermediates for chemical reactions: (1) generation in the presence of a reaction partner and (2) generation in the absence of a reaction partner with accumulation in solution as a "pool" followed by reaction with a subsequently added reaction partner. The former approach is more popular because reactive intermediates are usually short-lived transient species, but the latter method is more flexible and versatile. This review focuses on the latter approach and provides a concise overview of the current methods for the generation and accumulation of cationic reactive intermediates as a pool using modern techniques of electrochemistry and their reactions with subsequently added nucleophilic reaction partners.

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Thiofluorination of Carbon–Carbon Multiple Bonds Using Electrochemically Generated ArS(ArSSAr)+BF4−

Cited by 37 publications

References 32 publications

Organic reactions mediated by electrochemically generated ArS+

Organic reactions mediated by electrochemically generated ArS+

Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance

Electrogenerated Cationic Reactive Intermediates: The Pool Method and Further Advances

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