719-98-2Relevant articles and documents
Synthesis method of phthalimide type trifluoromethyl sulfuration reagent
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Paragraph 0020, (2021/06/02)
The invention belongs to the technical field of synthesis of organic compounds, and relates to a synthesis method of a phthalimide type trifluoromethyl sulfide reagent. The structural general formula of the reagent is as shown in the formula (1). The synthesis method of the phthalimide type trifluoromethyl sulfide reagent comprises the following steps: by taking a nitrogen halogenated compound containing a phthalimide structural framework, trifluoromethanesulfonate, nonafluorobutyl sulfonate, methanesulfonate and p-toluenesulfonate as reaction substrates, phthalimide type trifluoromethyl sulfuration reagent is synthesized by taking trifluoromethylthioester as a trifluoromethylthio source. According to the preparation method, trifluoromethylthioester is taken as a trifluoromethylthio source, trifluoromethylthio negative ions are generated under activation of fluorine negative ions, nucleophilic substitution is carried out on the reaction substrates, so that construction of a nitrogen-sulfur bond is realized, and the phthalimide type trifluoromethyl sulfuration reagent is obtained after separation and purification. According to the synthesis method of the phthalimide type trifluoromethyl sulfuration reagent, the raw materials are easy to prepare, the reaction reagent is low in price, the synthesis cost of the phthalimide type trifluoromethyl sulfide reagent is remarkably reduced, and industrial production is facilitated; synthesis conditions are mild, and operation is simple and safe; transition metal elements are not needed, and the method is green and environment-friendly.
Metal-free visible-light-enabled vicinal trifluoromethyl dithiolation of unactivated alkenes
Li, Xiaojuan,Zhang, Qiang,Zhang, Weigang,Ma, Jinzhu,Wang, Yi,Pan, Yi
supporting information, p. 551 - 557 (2021/03/31)
The difunctionalization of alkenes involving a trifluoromethylthio group (SCF3) for the conversion of versatile and readily available olefins into structurally more complex molecules has been successfully studied. However, the disproportionate dithiolation of alkenes is unknown. Herein, a transition-metal-free protocol is presented for the vicinal trifluoromethylthio-thiolation of unactivated alkenes via a radical process under mild conditions with a broad substrate scope and excellent tolerance.
Photocatalyzed Radical Relayed Regio- And Stereoselective Trifluoromethylthiolation-Boration
Zhang, Qiang,Li, Xiaojuan,Zhang, Weigang,Wang, Yi,Pan, Yi
supporting information, p. 5410 - 5414 (2021/07/21)
Vinylboronates and alkylboronates are key components in variegated transformations in all aspects of chemical science. This work describes a sequential radical difunctionalization strategy for the construction of fluorine-containing vinylboronates and alkylboronates with the integrated redox-active reagent N-trifluoromethylthiophthalimide. This multifunctional N-S precursor offers a scalable and practical protocol for the trifluoromethylthiolation-borylation of unsaturated hydrocarbons in a highly regio- and stereoselective fashion, which can be further converted into valuable synthons via boryl migration.
Asymmetric Synthesis of α-Trifluoromethylthio-β-Amino Acids under Phase Transfer Catalysis
Capaccio, Vito,Sicignano, Marina,Rodríguez, Ricardo I.,Della Sala, Giorgio,Alemán, José
supporting information, p. 219 - 223 (2019/12/30)
The first asymmetric α-trifluoromethylthiolation of 2-substituted isoxazolidin-5-ones was developed using Maruoka type N-spiro ammonium catalysts under phase-transfer conditions. The resulting products, containing a trifluoromethylthiolated quaternary chiral carbon, were obtained in moderate to good yields and up to 98:2 enantiomeric ratio. Moreover, the easy N-O bond cleavage provided access to undescribed α-trifluoromethylthio-β2,2-amino acids, with promising applications in biochemistry and medicinal chemistry.
Exploration of the Synthetic Potential of Electrophilic Trifluoromethylthiolating and Difluoromethylthiolating Reagents
Zhang, Jingjing,Yang, Jin-Dong,Zheng, Hanliang,Xue, Xiao-Song,Mayr, Herbert,Cheng, Jin-Pei
supporting information, p. 12690 - 12695 (2018/09/25)
The electrophilicity parameters (E) of some trifluoromethylthiolating and difluoromethylthiolating reagents were determined by following the kinetics of their reactions with a series of enamines and carbanions with known nucleophilicity parameters (N, sN), using the linear free-energy relationship log k2=sN(N+E). The electrophilic reactivities of these reagents cover a range of 17 orders of magnitude, with Shen and Lu's reagent 1 a being the most reactive and Billard's reagent 1 h being the least reactive electrophile. While the observed electrophilic reactivities (E) of the amido-derived trifluoromethylthiolating reagents correlate well with the calculated Gibbs energies for heterolytic cleavage of the X?SCF3 bonds (Tt+DA), the cumol-derived reagents 1 f and 1 g are more reactive than expected from the thermodynamics of the O?S cleavage. The E parameters of the tri/difluoromethylthiolating reagents derived in this work provide an ordering principle for their use in synthesis.
Method for preparing tertiary alkyl trifluoromethyl sulfide
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Paragraph 0024-0025, (2018/10/19)
The invention discloses a method for preparing tertiary alkyl trifluoromethyl sulfide. The method includes: using tertiary alkoxy ether as a raw material; under illumination of blue light, in a solution, in an argon atmosphere and at the presence of a small amount of potassium carbonate, reacting with 2-((trifluoromethyl)thio) isoindoline-1, 3-diketone at room temperature through synergistic catalysis of a photocatalyst 4CzIPN and an organic thiol catalyst 4-thionaphthol[2, 1-d:1', 2'-f][1, 3, 2]dioxocycloheptene-4-oxide, wherein the photocatalyst 4CzIPN and the organic thiol catalyst have following structures.
Preparation method for N-difluoromethylthiophthalimide compound
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Paragraph 0088-0092, (2018/03/01)
The invention discloses a preparation method for a N-difluoromethylthiophthalimide compound. The preparation method comprises a step of subjecting difluoromethanesulfonyl chloride and a compound as show in a formula 1 which is described in the specification to difluoromethylthiolation in an organic solvent so as to obtain the N-difluoromethylthiophthalimide compound as show in a formula 3 which isdescribed in the specification. The preparation method of the invention has the advantages of simple operation, few steps, a wide scope of applicable substrates, mild reaction conditions, a high reaction conversion rate, high yield, low cost and suitability for industrial production.
Organocatalytic Α-trifluoromethylthiolation of silylenol ethers: Batch vs continuous flow reactions
Abubakar, Said Said,Benaglia, Maurizio,Rossi, Sergio,Annunziata, Rita
, p. 94 - 101 (2017/09/25)
This work describes the organocatalytic α-trifluoromethylthiolation of silylenol ethers using N-(trifluoromethylthio)saccharin as trifluoromethylthiolating reagent that is activated by the presence of catalytic amounts of a Lewis base. Tetrahydrothiophene was identified as the best organocatalyst and it was successfully employed to promote the synthesis of different α-trifluoromethylketones; the reaction has been performed under a traditional batch methodology and under continuous flow conditions. In general, yields obtained using the traditional batch process were higher than those observed when the reaction was performed under flow conditions. However, short reaction times, higher productivity and higher space time yields were observed when a flow system process was employed. Preliminary DFT calculations were also performed in order to elucidate the mechanism of the reaction.
Preparation of Electrophilic Trifluromethylthio Reagents from Nucleophilic Tetramethylammonium Trifluoromethylthiolate
Kovács, Szabolcs,Bayarmagnai, Bilguun,Goossen, Lukas J.
supporting information, p. 250 - 254 (2017/02/05)
A straightforward synthetic entry to the principal classes of electrophilic trifluoromethylthiolating agents is presented. It draws on inexpensive, shelf-stable tetramethylammonium trifluoromethylthiolate (Me4N–SCF3) as the SCF3source in the place of stoichiometric coinage metal-SCF3complexes. (Figure presented.).
1,4-Diazabicyclo[2.2.2]octane-Promoted Aminotrifluoromethylthiolation of α,β-Unsaturated Carbonyl Compounds: N-Trifluoromethylthio-4-nitrophthalimide Acts as Both the Nitrogen and SCF3 Sources
Xiao, Qing,He, Qijie,Li, Juncheng,Wang, Jun
supporting information, p. 6090 - 6093 (2016/01/09)
A novel difunctionalization reaction is described. It uses N-trifluoromethylthio-4-nitrophthalimide as the reagent, which serves as both the nitrogen and SCF3 sources. In the presence of DABCO (1,4-diazabicyclo[2.2.2]octane), the nitrogen and SCF3 groups can be incorporated into α,β-unsaturated carbonyl compounds easily and give versatile β-amino ketones and esters in good yields. This difunctionalization reaction features mild reaction conditions, high atom-economy, and efficient access to α-SCF3 amino acids.
