Phenyl(trifluoroethyl)iodonium-triflate-initiated ring-opening polymerization of tetrahydrofuran

Fluoroalkylations and Fluoroalkenylations with Iodonium Salts

“…Regarding the reactivity of fluoroalkyliodonium salts, in their pioneer work, Umemoto and Gotoh showed that simple nucleophiles such as primary and secondary amines, alcohols, carboxylates, thiols, enolates or enol-ethers reacts straightforwardly with the electrophilic trifluorethylating reagent (3) and their reaction provide the corresponding 2,2,2-trifluoroethyl substituted derivatives (25)(26)(27)(28)(29)(30)(31)(32)(33) under transition-metal free conditions (Scheme 6). [13c,18] The reactions take place in dichloromethane solvent at 25 °C in short reaction time, and the N-, O-and Strifluoroethylated products (25)(26)(27)(28)(29)(30)(31) were obtained in high yields. Reactions with C-nucleophiles (32,33) are rather challenging, while the efficiency of the trifluoroethylation in these cases were relatively lower compared to the heteroatom nucleophiles.…”

“…(Scheme 15). [29] Terminating cationic species with water at room temperature afforded polytetrahydrofuran (polyTHF) containing trifluoroethoxy group at one end and hydroxy group at the other end of the polymer chain, which allowing further derivatisations. With the set of reaction parameters including temperature, concentration of 3 and reaction time, the efficiency of the polymerization and the average molecular weight of polymeric product was controlled and final products were obtained with high number average molecular weight in moderate to good yields.…”

Recent advances in trifluoroethylation reaction

“…118 In 2021, Zhang's group developed a method for the synthesis of CF 3 CH 2 -terminated polytetrahydrofuran via ring-opening polymerization of tetrahydrofuran with phenyl(trifluoroethyl)iodonium triflate (Scheme 56). 119 The number-average molecular weight and yield of the polymerized product varied with the reaction temperature, time, and the concentration of phenyl(trifluoroethyl)iodonium triflate. Addition of the radical inhibitor TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) to the reaction did not influence the formation of the product.…”

Effect of Lithium Salt on Lithium-Mediated Ammonia Synthesis

“…The previous study showed that the triflate can initiate the ring-opening polymerization of THF. 36 The performance of LiTFSI in diglyme was also evaluated under similar conditions. The CP curve indicates that the anode potential gradually increases to over 1 V vs Pt after a 30 min test, similar to the behavior observed when using THF as the solvent (Figure S20).…”

“…Another pathway for the formation of poly-THF is through the catalysis of THF polymerization by HTFSI (Figure S18). The previous study showed that the triflate can initiate the ring-opening polymerization of THF . The performance of LiTFSI in diglyme was also evaluated under similar conditions.…”