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Upstream product

• 2314-97-8 iodotrifluoromethane 
• 4892-02-8 Methyl thiosalicylate 
• 2926-29-6 Langlois reagent 
• 887144-97-0 Togni's reagent 
• 1140280-85-8 2-diazo-1-phenyl-2-((trifluoromethyl)sulfonyl)ethan-1-one 
• 610-97-9 o-iodo-methyl-benzoic acid 
• 811-68-7 silver(I) trifluoromethanethiolate 
• 610-94-6 2-bromobenzoic acid methyl ester 
• 81290-20-2 (trifluoromethyl)trimethylsilane 
• 1413732-47-4 (2,2'-bipyride-kN₁,kN₁')(1,1,1-trifluoromethanethiolato-kS)-copper 

Relevant academic research and scientific papers

Electrochemical Trifluoromethylation of Thiophenols with Sodium Trifluoromethanesulfinate

We developed an electrochemical trifluoromethylation of thiophenols without the use of metal catalysts and oxidants. This reaction features mild reaction conditions, readily available substrate, as well as moderate to good yields. In addition, this protocol can be easily scaled up with moderate efficiency.

Difluoro(aryl)(perfluoroalkyl)-λ4-sulfanes and Selanes: Missing Links of Trichloroisocyanuric Acid/Potassium Fluoride Chemistry

The TCICA/KF approach to oxidative fluorination of heteroatoms has emerged as a surprisingly simple, safe, and versatile surrogate to classically challenging fluorination reactions. Although polyfluorination (or chlorofluorination) of diaryl disulfides, diaryl diselenides, diaryl ditellurides, aryl iodides, and aryl(perfluoroalkyl)tellanes has been described, the application of this TCICA/KF methodology to aryl(perfluoroalkyl)sulfanes and selanes remains an area of unexplored chemical space. Accordingly, to address the “missing links” in the developing series of chalcogen-based substrate reactivity, we report mild syntheses of metastable difluoro(aryl)(perfluoroalkyl)-λ4-sulfanes and selanes. As only limited examples of these species exist in the current literature (accessible only by using F2 or XeF2/HF), we have carried out detailed structural analyses, primarily using NMR and SC-XRD data. In addition, we investigate the effect of the perfluoroalkyl chain on the outcome of oxidative fluorination, and, finally, we provide preliminary evidence that difluoro(aryl)(trifluoro-methyl)-λ4-sulfanes may act as fluorinating reagents.

2-Diazo-1-phenyl-2-((trifluoromethyl)sulfonyl)ethan-1-one: Another Utility for Electrophilic Trifluoromethylthiolation Reactions

2-Diazo-1-phenyl-2-((trifluoromethyl)sulfonyl)ethan-1-one (diazo-triflone) (2) is not only a building block but also a reagent. In this study, diazo-triflone, which was originally used for the synthesis of β-lactam triflones as a trifluoromethanesulfonyl

Copper-Catalyzed Trifluoromethylthiolation of Di(hetero)aryl-λ3-iodanes: Mechanistic Insight and Application to Synthesis of (Hetero)Aryl Trifluoromethyl Sulfides

The direct and regioselective copper/S-Phos-catalyzed trifluoromethylthiolation of symmetrical and unsymmetrical di(hetero)aryl-λ3-iodanes has been accomplished for the synthesis of various (hetero)aryl trifluoromethyl sulfides employing readily accessible silver trifluoromethylthiolate (AgSCF3) as nucleophilic trifluoromethylthiolating reagent. The developed transformation tolerates various functional groups like nitrile, enolizable ketone, ester, nitro and free carboxylic acid. Interestingly, the formal trifluoromethylthiolation of arenes was also achieved through integration of the synthesis of diaryl-λ3-iodanes from arenes with the trifluoromethylthiolation. Mechanistic investigations did not favor the radical formation and SET pathway. Based on the variable temperature 19F NMR spectroscopy, isolation of the most relevant catalytic intermediate, and stoichiometric studies supported the Cu(I)/Cu(III) catalytic cycle, wherein the oxidative addition of diaryl-λ3-iodanes was assisted by the silver salt.

Trifluoromethylthiolation of aryl iodides and bromides enabled by a bench-stable and easy-to-recover dinuclear palladium(I) catalyst

Abstract While palladium catalysis is ubiquitous in modern chemical research, the recovery of the active transition-metal complex under routine laboratory applications is frequently challenging. Described herein is the concept of alternative cross-coupling cycles with a more robust (air-, moisture-, and thermally-stable) dinuclear PdI complex, thus avoiding the handling of sensitive Pd0 species or ligands. Highly efficient C-SCF3 coupling of a range of aryl iodides and bromides was achieved, and the recovery of the PdI complex was accomplished via simple open-atmosphere column chromatography. Kinetic and computational data support the feasibility of dinuclear PdI catalysis. A novel SCF3-bridged PdI dimer was isolated, characterized by X-ray crystallography, and verified to be a competent catalytic intermediate. Pd double team: The cross-coupling enabled by an air-, moisture-, and thermally stable dinuclear PdI complex was explored. Highly efficient C-SCF3 coupling of a range of aryl iodides and bromides was achieved and the catalyst was recovered by simple column chromatography, thus highlighting its robustness and the possibility for catalyst recycling. Kinetic and computational data support the feasibility of dinuclear PdI catalysis.

Copper-catalyzed synthesis of aryl and alkyl trifluoromethyl sulfides using CF3SiMe3and Na2S2O3as -SCF3source

A universal and efficient Cu(I)-catalyzed synthesis of aryl and alkyl trifluoromethyl sulfides has been developed. In this catalytic system, S-aryl or S-alkyl sulfothioate (I or II) proved to be the key intermediate. Substrates bearing groups of I, Br, Cl, OTs, and OMs on the aryl carbon and no matter electron-withdrawing and electron-donating substitutions on the aromatic ring could afford good to excellent yields.

Copper-catalyzed trifluoromethylthiolation of aryl halides with diverse directing groups

The expansion of cross-coupling components in Cu-catalyzed C-X bond forming reactions have received much attention recently. A novel Cu-catalyzed trifluoromethylthiolation of aryl bromides and iodides with the assistance of versatile directing groups such as pyridyl, methyl ester, amide, imine and oxime was reported. CuBr was used as the catalyst, and 1,10-phenanthroline as the ligand. By changing the solvent from acetonitrile to DMF, the coupling process could even take place at room temperature.

An air-stable copper reagent for nucleophilic trifluoromethylthiolation of aryl halides

A series of copper(I) trifluoromethyl thiolate complexes have been synthesized from the reaction of CuF2 with Me3SiCF 3 and S8 (see scheme; Cu red, F green, N blue, S yellow). These air-stable complexes serve as reagents for the efficient conversion of a wide range of aryl halides into the corresponding aryl trifluoromethyl thioethers in excellent yields. Copyright

Convenient synthesis and isolation of trifluoromethylthio-substituted building blocks

Various aryl-, heteroaryl-, and alkyl mercaptanes (RSH, 1a-r) were treated with a slight excess of NaH suspended in DMF to make the appropriate sodium thiolates (RSNa), which then reacted with 1.3 equivalent of CF3I at room temperature for overnight to afford the appropriate trifluoromethyl sulfides (CF3SR, 2) in fair to good yields. The radical chain alkylation reaction was effective without the use of UV irradiation with all but three substrates (thiosalicylic acid, 1k; 2-mercaptobenzimidazole, 1q; and 3-mercaptopropionic acid, 1r). Steam-distillation was found as an effective and easy to upscale means for the isolation of these volatile and water immiscible sulfides. The CF3I reagent gas was conveniently weighed and delivered to the reaction mixture by the balloon technique or as a preliminary made stock solution in DMF or DMSO. The sulfides 2 obtained here were assayed by GC and characterized by 1H, 13C, 19F NMR and MS spectroscopy.