Syntheses and reactions of polyfluoroalkyl fluorosulfates

Abstract

Several polyfluoroalkyl fluorosulfates, RfOS02F (Rf = CF3CH(CH3), CF3C(CH3)2, and (CF3)2CH), have been synthesized by the reaction of polyfluoro alcohols with sulfuryl fluoride or sulfuryl chloride fluoride. They reacted with nucleophilic reagents such as amines, polyfluoro alcohols, polyfluoroalkoxides and bromide ion to give sulfamates, dialkyl sulfates, and polyfluoroalkyl bromides, respectively. In the case of CF3(CH3)2C0S02F with bromide ion, the polyfluoroalkyl bromide loses hydrogen bromide to give 2-(trifluoromethyl)propene in high yield.The presence of three electrophilic centers in polyfluoroalkyl fluorosulfates and chlorosulfates,1 carbon, sulfur, and fluorine (chlorine), render the Rf0S02X (X = Cl, F) substrates of considerable interest because nucleophiles may potentially react at one or several of these centers. It is well known that perfluoroalkyl and polyfluorohaloalkyl fluorosulfates undergo facile attack by nucleophiles such as fluoride ion, ammonia, or methanol to cleave the S-0 bond to form ketones (eq l),2 amides (eq 2),3 or esters (eq 3).4

Sulfur(VI) Fluoride Exchange (SuFEx): Another Good Reaction for Click Chemistry

“…[120] In addition, certain perfluorinated aliphatic fluorosulfates can be isolated and were shown to form stable sulfate and sulfamate connections. [121] The simple reaction of SO 2 F 2 with alcohols reaches its zenith for aromatic substrates, since the derived aryloxyfluorosulfates are very stable. Even more importantly for biological applications, aromatic alcohols undergo selective modification by SO 2 F 2 gas, leaving aliphatic alcohols, aliphatic and aromatic amines, and carboxylates untouched.…”

Synthesis and Chemical Transformations of Fluorosulfates

“…Huang and Shreeve synthesized 1,1,1‐trifluoroisopropyl fluorosulfate ( 64 ) from the reaction of 1,1,1‐trifluoro‐2‐propanol ( 63 ) with sulfuryl chloride fluoride and trimethylamine (Scheme ) …”

Schwefel(VI)‐fluorid‐Austausch (SuFEx): Eine weitere gute Anwendung für die Click‐Chemie

“…[120] Auch perfluorierte aliphatische Fluorsulfate wurden isoliert, für die gezeigt wurde, dass sie stabile Sulfat-und Sulfamatbindungen bilden. [121] Die einfache Reaktion von SO 2 F 2 mit Alkoholen erreicht ihren Zenit bei aromatischen Substraten, da die so erhaltenen Aryloxyfluorsulfate sehr stabil sind. Noch wichtiger für biologische Anwendungen ist, dass aromatische Alkohole eine selektive Modifikation mit SO 2 F 2 -Gas durchlaufen, wobei aliphatische Alkohole, aliphatische und aromatische Amine und Carboxylate unberührt bleiben.…”