6476-52-4

Upstream product

• 421-17-0 Trifluoromethylsulfenyl chloride 
• 110-82-7 cyclohexane 
• 14999-80-5 trifluoromethyl pentafluorophenyl disulfide 
• 1494-06-0 bis(pentafluorophenyl) disulfide 
• 2550-40-5 1,2-dicyclohexyl disulfide 
• 2926-29-6 Langlois reagent 
• 81290-20-2 (trifluoromethyl)trimethylsilane 
• 4251-13-2 thiocyanatocyclohexane 
• 75-09-2 dichloromethane 
• 75-46-7 trifluoromethan 
• 289706-46-3 4-[2,2,2-trifluoro-1-(trimethylsilyloxy)ethyl]morpholine 
• 321573-95-9 1-benzyl-4-(2,2,2-trifluoro-1-(trimethylsilyloxy)ethyl)piperazine 
• 108-98-5 thiophenol 
• 1493-15-8 trifluoromethylsulfide 

Relevant academic research and scientific papers

A New Approach for the Synthesis of Perfluoroalkanesulfenic Acids

A new and more practical method for the preparation of solution-stable perfluoroalkanesulfenic acids was successfully developed. Starting from perfluoroalkyl iodides, perfluoroalkyl sulfoxides were synthesized by their substitution reaction with alkyl mercaptans and the following oxidation of resulting perfluoroalkyl sulfides with m-CPBA. Subsequent β-H elimination of perfluoroalkyl sulfoxides under heating conditions gave the corresponding perfluoroalkanesulfenic acids in good yields.

Catalyst-Free Decarbonylative Trifluoromethylthiolation Enabled by Electron Donor-Acceptor Complex Photoactivation

A catalyst- and additive-free decarbonylative trifluoromethylthiolation of aldehyde feedstocks has been developed. This operationally simple, scalable, and open-to-air transformation is driven by the selective photoexcitation of electron donor-acceptor (EDA) complexes, stemming from the association of 1,4-dihydropyridines (donor) with N-(trifluoromethylthio)phthalimide (acceptor), to trigger intermolecular single-electron transfer events under ambient- and visible light-promoted conditions. Extension to other electron acceptors enables the synthesis of thiocyanates and thioesters, as well as the difunctionalization of [1.1.1]propellane. The mechanistic intricacies of this photochemical paradigm are elucidated through a combination of experimental efforts and high-level quantum mechanical calculations [dispersion-corrected (U)DFT, DLPNO-CCSD(T), and TD-DFT]. This comprehensive study highlights the necessity for EDA complexation for efficient alkyl radical generation. Computation of subsequent ground state pathways reveals that SH2 addition of the alkyl radical to the intermediate radical EDA complex is extremely exergonic and results in a charge transfer event from the dihydropyridine donor to the N-(trifluoromethylthio)phthalimide acceptor of the EDA complex. Experimental and computational results further suggest that product formation also occurs via SH2 reaction of alkyl radicals with 1,2-bis(trifluoromethyl)disulfane, generated in-situ through combination of thiyl radicals. (Figure presented.).

Ionic Liquids for Fast and Solvent-Free Nucleophilic Trifluoromethylthiolation of Alkyl Halides and Alcohols

The trifluoromethylthio group is of rising interest in medicinal, agrochemical, and materials chemistry. Although several strategies for the introduction of this functional group have been described, new synthetic methods are needed. A novel ionic liquid, 1-n-butyl-3-methylimidazolium trifluoromethylthiolate, has been developed and is herein reported as an efficient and recyclable in situ generated trifluoromethylthiolating reagent for alkyl halides, sulfonates, and even unactivated alcohols under solvent-free conditions.

Oxidative decarboxylative radical trifluoromethylthiolation of alkyl carboxylic acids with silver(i) trifluoromethanethiolate and selectfluor

A straightforward silver-mediated oxidative decarboxylative radical trifluoromethylthiolation reaction of aliphatic carboxylic acid is described. This reaction operates under mild conditions and allows the synthesis of various valuable alkyltrifluoromethylthioethers from abundant alkyl carboxylic acids and convenient nucleophilic AgSCF3 reagent. It provides a practical and efficient approach for the preparation of alkyltrifluoromethylthioethers.

Alkyl trifluoromethyl sulfide compound and its preparation method

The invention discloses an alkyl trifluoromethyl thioether compound and a preparation method thereof. The alkyl trifluoromethyl thioether compound comprises the following step: under protection of inertial gas, carrying out trifluoromethylthiolation reaction on an alkyl primer and a trifluoromethylthio reagent to obtain the alkyl trifluoromethyl thioether compound. The trifluoromethylthio reagent comprises the following components: a metal salt containing trifluoromethylthio, an oxidizing agent and a nitrile solvent. The trifluoromethylthio reagent disclosed by the invention is low in price and easily available. When the trifluoromethylthio reagent is used for synthesizing the alkyl trifluoromethyl thioether compound, the trifluoromethylthio can be quickly and conveniently introduced to the alkyl primer which is not pre-functionalized. Moreover, the synthetic method is wide in range of application of the primer, mild in reaction condition, high in reaction efficiency, mostly direct in reaction, simple to operate, low in cost and more suitable for industrial production.

Approach to Comparing the Functional Group Tolerance of Reactions

Herein, we describe an approach to quantifying and comparing functional group (FG) tolerance of synthetic reactions. Additive-based reaction screening is utilized as a tool for the objective comparison of reaction conditions as demonstrated in four case studies. This contributes to an understanding of factors limiting a reaction's FG tolerance and the identification of truly mild reactions.

Visible-Light-Promoted Activation of Unactivated C(sp3)-H Bonds and Their Selective Trifluoromethylthiolation

Selective functionalization of ubiquitous C(sp3)-H bonds using visible light is a highly challenging yet desirable goal in organic synthesis. The development of such processes relies on both rational design and serendipitous discoveries from innovative tools such as screening technologies. Applying a mechanism-based screening strategy, we herein report photoredox-mediated hydrogen atom transfer catalysis for the selective activation of otherwise unactivated C(sp3)-H bonds, followed by their trifluoromethylthiolation, which has high potential as a late-stage functionalization tool. The generality of this method is exhibited through incorporation of the trifluoromethylthio group in a large number of C(sp3)-H bonds with high selectivity without the need for an excess of valuable substrate.

Silver-mediated oxidative aliphatic C-H trifluoromethylthiolation

The first example of a practical and direct trifluoromethylthiolation reaction of unactivated aliphatic C-H bonds employs a silver-based reagent. The reaction is operationally simple, scalable, and proceeds under aqueous conditions in air. Furthermore, its broad scope and good functional-group compatibility were demonstrated by applying this method to the selective trifluoromethylthiolation of natural products and natural-product derivatives.

Direct trifluoromethylthiolation of unactivated C(sp3)-H using silver(I) trifluoromethanethiolate and potassium persulfate

A practical and efficient method for the direct trifluoromethylthiolation of unactivated C(sp3)-H bonds by AgSCF3/K2S2O8 under mild conditions is described. The reaction has a good functional-group tolerance and good selectivity. Initial mechanistic investigations indicate that the reaction may involve a radical process in which K2S2O8 plays key roles in both the activation of the C(sp3)-H bond and the oxidation of AgSCF3.

Metal-Free Trifluoromethylthiolation of Alkyl Electrophiles via a Cascade of Thiocyanation and Nucleophilic Cyanide-CF3 Substitution

A straightforward synthesis of alkyl trifluoromethyl thioethers was developed that starts from widely available alkyl halides or mesylates and the inexpensive reagents sodium thiocyanate and trimethyl(trifluoromethyl)silane. The alkyl electrophiles are converted in situ into the corresponding thiocyanates, which react with the nucleophilic Ruppert-Prakash reagent to give the corresponding trifluoromethyl thioethers via a Langlois-type CN-CF3 substitution. This process enables the efficient introduction of the pharmaceutically meaningful trifluoromethylthio groups into functionalized molecules without the need of metal catalysts or expensive preformed trifluoromethylthiolating agents.