Synthesis And Application Of S-(trifluoromethyl)diphenylsu-Lfonium Triflate

Objective: This dissertation describes the synthesis and application of S-(trifluorom-ethyl)diphenylsulfonium triflate. The reaction mechanisms were investigated in detail.Methods: S-(trifluoromethyl)diphenylsulfonium triflate was synthesized from thereaction of trifluoromethylsulfinate with triflic anhydride. Trifluoromethylsulfinatewas prepared by sulfinatodebromination of bromotrifluoromethane. The reactions ofS-(trifluoromethyl)diphenylsulfonium triflate with terminal alkynes and styrenes inthe presence of metals were then investigated.Results: S-(trifluoromethyl)diphenylsulfonium triflate can react with Cu(I) togenerate Cu(III) intermediate, which was assumed to be the most probableintermediate in the reaction of sulfonium triflate with cuprous iodide and terminalalkynes. Trifluoromethylated terminal alkynes were obtained via reductiveelimination. Moreover, S-(trifluoromethyl)diphenylsulfonium triflate can be reducedby cuprous iodide to form CF3radical. The CF3radical can be captured by styrenes,giving trifluoromethylate styrenes in an inert atmosphere and anhydrous environmentvia deprotonation. S-(trifluoromethyl)diphenylsulfonium triflate can react withstyrenes in the presence of cuprous iodide and water to generate trifluorophenylpropylformate unexpectedly in N,N-dimethylformamide.Conclusion: S-(trifluoromethyl)diphenylsulfonium triflate was demonstrated to beeffective electrophilic trifluoromethylation reagent. It can react with Cu(I) throughoxidative addition or signal electron transfer. In addition, the efficient methods weredeveloped for the trifluoromethylation of terminal alkynes and styrenes.