β-Trifluorosulfinylesters: tuneable reagents for switchable trifluoromethylsulfinylation and C–H trifluoromethylthiolation

Abstract

beta-Trifluorosulfinylesters, a family of novel reagents for direct trifluoromethylthiolation and trifluoromethylsulfinylation were developed. The reagents were easily prepared in three step steps without column purification from inexpensive commercially available starting...

Direct transfer of a trifluoromethylsulfinyl group by a general reagent N-trifluoromethylsulfinylphthalimide under a catalytic or stoichiometric Lewis acid or Lewis base

“…20 Then in 2023, Shao et al developed a novel nucleophilic trifluoromethylsulfinylation with aromatics or aryl high-valent iodine substrates via β-trifluorosulfinylesters. 21 Furthermore, examples of trifluoromethyl sulfoxides generated from the rearrangement of allylic alcohols/ketoximes and electrophilic SCF 3 donors have also been reported. 22 However, until recently, the choice of direct electrophilic trifluoromethylsulfinylating reagents for multitudinous nucleophiles (C, N, O) remained sparse.…”

Lewis base-catalyzed trifluoromethylsulfinylation of alcohols and phenols: modular synthesis of trifluoromethanesulfinate esters

“…9 In 2023, our group disclosed that β-trifluorosulfinylesters could serve as tunable reagents for the selective trifluoromethylsulfinylation of diaryliodonium salts or trifluoromethylthiolation of electron-rich arenes and alkenes. 10 Therefore, it will be meaningful to prepare fluorinated sulfoxides efficiently and develop practical methods to apply these hypervalent sulfur scaffolds in organic synthesis and drug discovery.…”

Synthesis and Electrophilic Trifluoromethylthiolation Properties of 1-Methyl-4-(trifluoromethylthio)piperazine (MTTP)

“…More recently, a slew of additional reagents were reported, including N-trifluoromethylthiodibenzenesulfonimide XII 27 (Shen and Zhao), trifluoro-methyl sulfoxide XIII 28 (Proctor), hypervalent iodine XIV 29 (Zhang), Hu's XV 30 and Shao's β-trifluorosulfinylester XVI. 31 Their usefulness notwithstanding, these reagents have shortcomings, including instability, toxicity, reliance on expensive or hazardous precursors, multistep synthesis, low atom-economy, or narrow application scope. Of particular concern to us was that their utilization in the direct C−H trifluoromethylthiolation of arenes was circumscribed to electron-rich or activated arenes, 17,21,23,26−29,31−35 except in a single case (bromobenzene), which was trifluoromethylthiolated with CF 3 SO 2 Na/Tf 2 O, but in low yield.…”

“…Commercially available CF 3 SO 2 Na X and CF 3 SO 2 Cl XI have also been employed. More recently, a slew of additional reagents were reported, including N -trifluoromethylthiodibenzenesulfonimide XII (Shen and Zhao), trifluoro-methyl sulfoxide XIII (Proctor), hypervalent iodine XIV (Zhang), Hu’s XV and Shao’s β-trifluorosulfinylester XVI . Their usefulness notwithstanding, these reagents have shortcomings, including instability, toxicity, reliance on expensive or hazardous precursors, multistep synthesis, low atom-economy, or narrow application scope.…”

“…Their usefulness notwithstanding, these reagents have shortcomings, including instability, toxicity, reliance on expensive or hazardous precursors, multistep synthesis, low atom-economy, or narrow application scope. Of particular concern to us was that their utilization in the direct C–H trifluoromethylthiolation of arenes was circumscribed to electron-rich or activated arenes, ,,,− ,− except in a single case (bromobenzene), which was trifluoromethylthiolated with CF 3 SO 2 Na/Tf 2 O, but in low yield . Our group recently reported an easy-to-handle, one-step preparation of TTST XVII, a highly versatile and atom-economic reagent (Figure A).…”