SuFEx‐Based Polysulfonate Formation from Ethenesulfonyl Fluoride–Amine Adducts

Abstract

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One-pot synthesis of polysulfonate by a cascading sulfur(vi) fluorine exchange (SuFEx) reaction and cyanosilylation of aldehyde

“…As shown in Table 2, the effect of the reaction temperature on the polymerization reaction (entries 1-5) was evaluated by choosing N,N-dimethylformamide (DMF) as a solvent and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as a catalyst referring to the previous literature. 13 First, the two monomers reacted at a molar ratio of 1 : 1 at room temperature.…”

“…Methosilyl fluoride, the inert by-product of the reaction, is also useful and very easy to remove, which makes the SuFEx reaction greener and simpler. The SuFEx reaction has been used to synthesize new polymers with high and low molecular weight distribution efficiently, such as polysulfate, 9,12 polysulfonate [13][14][15] and polysulfonamide. 16 In addition, the SuFEx reaction has also been applied in synthetic methodology, 17-20 biochemistry, [21][22][23][24] optoelectronic polymers, [25][26][27] liquid crystal polymers, 28 and surface modification.…”

Radical 1‐Fluorosulfonyl‐2‐alkynylation of Unactivated Alkenes

“…[5] In general, sulfonyl fluorides can be prepared by fluoride-chloride-exchange from the corresponding sulfonyl chlorides that are obtained from thiols, halides or sultones. [3] Other methods for the preparation of sulfonyl fluorides use conjugate additions [14,15] or cycloadditions [16] on sulfonyl fluoride containing Michael acceptors. Considering radical chemistry, Liu et al developed a method for the trifluoromethylfluorosulfonylation of unactivated alkenes that uses a super stoichiometric amount of Ag salt as a CF 3radical and a SO 2 -precursor along with NFSI.…”

“…[4a, 12] Moreover, sulfonyl fluorides have also found use in polymer science. [13,14] These works aimed for the identification of new modular connective hubs such as sulfuryl fluoride, thionyl tetrafluoride, ethene sulfonyl fluoride (ESF), 1-bromoethene-1-sulfonyl fluoride (BESF) and 2-substituted-alkynyl-1-sulfonyl fluorides (SASF) (see Scheme 1a). [5] In general, sulfonyl fluorides can be prepared by fluoride-chloride-exchange from the corresponding sulfonyl chlorides that are obtained from thiols, halides or sultones.…”

Radikalische 1‐Fluorsulfonyl‐2‐alkinylierung von nicht aktivierten Alkenen

“…[5] Sulfonylfluoride lassen sich durch Fluorid-Chlorid-Austausch aus den entsprechenden Sulfonylchloriden herstellen, welche aus Thiolen, Halogeniden oder Sultonen gewonnen werden können. [3] Andere Methoden zur Darstellung von Sulfonylfluoriden nutzen konjugate Additions- [14,15] oder Cycloadditionsreaktionen [16] an Michael-Akzeptoren, die be-reits eine Sulfonylfluorid-Einheit enthalten. Hinsichtlich radikalchemischer Transformationen wurde von Liu et al eine Methode für die Trifluormethylfluorsulfonylierungsreaktion von nicht aktivierten Alkenen entwickelt, bei der eine überstöchiometrische Menge eines Ag-Salzes als CF 3 -Radikal und SO 2 -Vorläufer in Kombination mit NFSI verwendet wird.…”