Oxidative fluorination in the Ph₂SO–XeF₂–Cl⁻ system and fluorine exchange in the Ph₂S(O)F₂–Ph₂S(O)F⁺ system

Abstract

Oxidative fluorination of diphenyl sulfoxide with xenon difluoride occurs under mild conditions in the presence of

(Hetero)aryl‐SVI Fluorides: Synthetic Development and Opportunities

“…At this point, two pathways can be envisaged. As already reported by Janzen and Ou, [22,23] chlorine radicals (or Cl 2 ) and fluoride anions are formed when XeF 2 is mixed with chloride anions. Therefore, in path a (Scheme 15), fluoride anions react with Lewis acidic ArÀ SF 3 , and after oxidation and radical coupling with a Scheme 12.…”

(Hetero)aryl‐SVI Fluorides: Synthetic Development and Opportunities

“…At this point, two pathways can be envisaged. As already reported by Janzen and Ou, [22,23] chlorine radicals (or Cl 2 ) and fluoride anions are formed when XeF 2 is mixed with chloride anions. Therefore, in path a (Scheme 15), fluoride anions react with Lewis acidic ArÀ SF 3 , and after oxidation and radical coupling with a chlorine radical, the trans isomer is formed.…”

“…Mechanistically, it was postulated that a Cl-mediated activation of XeF 2 for the oxidative fluorination of diarylsulfoxides would initiate the reaction, which would be followed by a radical chain reaction propagated by Ph 2 S(O * )F species. [23] In 2016, Stephan and co-workers developed a variety of diaryl fluorosulfoxonium cations (24)(25)(26)(27) and applied them to several Lewis acid catalyzed reactions (Scheme 7). [24] Synthetically inspired by the procedure developed by Janzen and Ou, Stephan and co-workers were able to oxidize diaryl sulfoxides Similarly, in 2021 Panossian and co-workers applied Lewis acidic sulfoxonium cation 25 in ring-opening [3+2] and [4+2] annulations (Scheme 8).…”

Chemistry of xenon derivatives. Synthesis and chemical properties

“…Apparently, the chloride anion promotes the generation of the fluoride anion, which behaves as a strong base in CH 2 Cl 2 in the absence of HF. 386,387 The reaction mechanism proposed by Ou and Janzen 385 which includes the formation of the anion 228 and its oxidation to the radicals 229 ± 231 is corroborated experimentally by the identification of the radical XeF . (spectroscopic data).…”

“…384 The reaction of Ph 2 SO with XeF 2 in the presence of *1% solution of Et 4 NCl in CH 2 Cl 2 at 20 8C results in the difluoride 217 in quantitative yield. 385 In the absence of Cl 7 , the reaction is sluggish (2 ± 6 days). Apparently, the chloride anion promotes the generation of the fluoride anion, which behaves as a strong base in CH 2 Cl 2 in the absence of HF.…”