Chemistry of ethenesulfonyl fluoride. Fluorosulfonylethylation of organic compounds

An entirely new methodology for synthesizing perfluorinated compounds: synthesis of perfluoroalkanesulfonyl fluorides from non-fluorinated compounds

“…Reaction of 2-chloroethanesulfonyl fluoride 11 [14], which is a derivative of isethionic acid, with the sodium salt of ethylene glycol gave the substrate 12 of the PERFECT process as shown in Scheme 3. Esterification was carried out as in the usual PERFECT methodology to give partially fluorinated ester 13, although the yield was not satisfactory because the reaction of the sulfonyl fluoride group and the hydroxyl group in the structure also took place intramolecularly.…”

“…Ethylene glycol (141 g) and a methanol solution of sodium methoxide (28 wt.%, 96.4 g, 0.500 mol) were charged and stirred, and heated under reduced pressure to distill off methanol to afford a solution of sodium salt of ethylene glycol. A solution of 11 [14] (50 g, 0.341 mol) in THF (100 mL) was stirred under cooling with ice bath, and the previously obtained solution of sodium salt of ethyleneglycol was dropwise added thereto over a period of 2.5 h, while maintaining the internal temperature to be at 10 8C. After completion of the dropwise addition, the reaction mixture was stirred at room temperature for 2 h. Then the reaction mixture was added to water (400 mL), extracted with dichloromethane, and the combined organic layer was dried over magnesium sulfate.…”

Pd-Catalyzed Mizoroki-Heck Reactions Using Fluorine-Containing Agents as the Cross-Coupling Partners

“…Ethenesulfonyl fluoride (ESF) is a highly reactive and versatile reagent in the synthesis of a wide variety of organosulfur compounds, which behaves as a strong Michael acceptor or a Diels-Alder dienophile to conveniently introduce an SO 2 F group [59]. In 2016, Wu and Sharpless described a Pd-catalyzed Heck-Matsuda process for the synthesis of the otherwise difficult to access β-arylethenesulfonyl fluorides (Scheme 8) [60].…”

Proteasome inhibition by new dual warhead containing peptido vinyl sulfonyl fluorides

“…[19] In agreement with the literature the first step is probably a Michael reaction of the amine (scheme 5). [18] Since a 7-membered ring is in general not easily accessible, its proposed formation in vivo may be challenging to mimic in vitro. Scheme 5.…”