trans-Trifluoromethyltetrafluorosulfanyl Chloride: Selective Synthesis and Reaction with Diazo Compounds

Abstract

trans-Trifluoromethyltetrafluorosulfanyl chloride (trans-CF3SF4Cl) is a unique reagent for the incorporation of the CF3SF4 group into organic compounds. However, CF3SF4Cl was prepared from hazardous reagents or formed as mixture of trans and cis isomers in low yield. Herein, a silver-promoted selective synthesis of trans-CF3SF4Cl under safe gas-reagent-free conditions is described. Furthermore, the synthetic application of trans-CF3SF4Cl is demonstrated through the new trifluoromethyltetrafluorosulfanylation of α-diazo carbonyl compounds.

Overcoming a Radical Polarity Mismatch in Strain‐Release Pentafluorosulfanylation of [1.1.0]Bicyclobutanes: An Entryway to Sulfone‐ and Carbonyl‐Containing SF5‐Cyclobutanes

“…Subsequently, we examined whether the aforementioned methods translate to tetrafluoro(aryl)sulfanylation or tetrafluoro(trifluoromethyl)sulfanylation of BCBs (Scheme 3, top and bottom panels ). Both aryl‐SF 4 Cl compounds and CF 3 SF 4 Cl are known to participate in radical chain propagation reactions a la SF 5 Cl [2a,9,25,26] and have recently become more accessible through corrosive gas reagent‐free syntheses [2,4a,27] . Yet, it cannot be assumed they will always react like SF 5 Cl.…”

Visible Light-Driven α-Diazoketones as Denitrogenated Synthons: Synthesis of Fluorinated N-Heterocycles via Multicomponent Cyclization Reactions

“…As a continuation of our interest in the construction of heterocycles, we envisioned using fluorination reagents to produce radicals via a photocatalytic process, which further underwent radical addition reactions with α-diazoketones to generate radical intermediate I . The difficulty was that intermediate I prevented the extraction of hydrogen atoms to provide fluoroalkylation products but promoted it undergoing a single-electron reduction and β-F elimination processes to generate fluoroolefin intermediate II . Finally, the fluoroolefin was transformed into CF 3 -containing heterocycles with N-nucleophiles (Scheme c).…”

Synthesis of trans-Tetrafluoro(trifluoromethyl)-λ6-sulfanyl (CF3SF4)-Containing Olefins via Cross Metathesis

“…The tetrafluoro(trifluoromethyl)-λ 6 -sulfanyl group (CF 3 SF 4 ) belongs to the same class of fluorinated functionality as the pentafluorosulfanyl (SF 5 ) and trifluoromethyl groups. Incorporation of the CF 3 SF 4 group into a molecule profoundly changes the physicochemical properties of the compound.…”

“…The chemistry of the trans -tetrafluoro­(trifluoromethyl)-λ 6 -sulfanyl group (CF 3 SF 4 ) is little explored. The preparation of tetrafluoro­(trifluoromethyl)-λ 6 -sulfanyl chloride (CF 3 SF 4 Cl) and the addition of CF 3 SF 4 Cl to aliphatic compounds was described in four accounts from the 1970s, − but recently, CF 3 SF 4 Cl addition reactions to alkenes and diazoalkanes have received considerable attention. On incorporation in peptides, the CF 3 SF 4 group has been shown to have remarkable effects on the secondary structure.…”