Trifluoromethyl diphenylsulfonium Triflate

Solubility soluble in DMF, DMSO, CH3CN, CH2CI2, slightly soluble in THE, 1,4-dioxane, and insoluble in Et20. 

Purification recrystaUized from ethyl acetate/hexanes. 

Handling, Storage, and Precautions nonhygroscopic and thermally stable crystals. Should be stored in a dry atmosphere. 

Preparative Method trifluoromethanesulfonic anhydride (17 mL, 0.100 mol) in benzene (20 mL, 0.220 mol) was added to a suspension of sodium trifluoromethanesulhnate (6.98 g, 44.7 mmol) in dichloromethane (5 mL) at 0 °C. After vigorously stirring at 0 °C for 1.5 h, the reaction mixture was warmed to room temperature and mixed for an additional 34 h. The reaction mixture then was diluted with CH2CI2 (150 mL), washed with saturated aq. NaHCOs and saturated brine, and dried over Na2 SO4. After concentration under reduced pressure, the residue was purihed by column chromatography on silica gel using dichloromethane/acetonitrile (4 1) as the eluent. 

Shanghai Institute of Organic Chemistry, Shanghai, China 

---

Kinetic Parameters for the Trifluoromethylation of Aniline with 5-(Trifluoromethyl)dibenzothiophenium Triflate (17), S-(Trifluoromethyl)diphenylsulfonium Triflate (29), AND 5-(Trifluoromethyl)-3,7-DINITRODIBENZOTHIOPHENIUM TrIFLATE (39) IN DMF-d7 AT 25°C... 

Trifluoromethyl)diphenylsulfonium triflate can be reduced by Cu metal, converting iodo-substituted aromatics and heteroaromatics into the corresponding trifluoromethylated compounds in high yield (eq 1). ... 

The reaction of (5)-(trifluoromethyl)diphenylsulfonium triflate with Na2S204 or H0CH2S02Na under suitable conditions can generate the CF3 radical without further reduction. Various styrenes react with (5)-(trifluoromethyl)diphenylsulfonium triflate in the presence of H0CH2S02Na-2H20 or Na2S204, furnishing a-trifluoromethylated ketones (eq 4). ... 

In a recent paper, 5-(trifluoromethyl)diphenylsulfonium triflate (545) in the presence of copper was proposed as an efficient reagent for trifluoromethylation of heteroaromatic compounds [282]. In particular, 3-chloro-6-iodopyridazine smoothly reacted with this reagent to give the product of the iodine selective substitution (546) in 98 % yield (Scheme 109). The proposed mechanism for the formation of active species included reduction of 545 leading to trifluoromethyl radicals, which in turn reacted with copper to give CFjCu. 

---