- Copper-Mediated Trifluoromethylthiolation of Heteroaryl Bromides
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An efficient protocol for the copper-mediated trifluoromethylthiolation of heteroaryl bromides has been achieved using the copper complex (bpy)Cu(SCF3) as trifluoromethylthiolating reagent. This procedure provides a straightforward synthetic method for heteroaryl trifluoromethyl sulfides from readily available, simple starting materials. The reaction demonstrates a broad substrate scope and tolerates a wide array of functional groups, including nitrile, ester, chloro, nitro, or methoxy substituents.
- Zhang, Mengjia,Weng, Zhiqiang
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Read Online
- Radical Fluoroalkylation of Isocyanides with Fluorinated Sulfones by Visible-Light Photoredox Catalysis
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The radical fluoroalkylation of isocyanides with fluorinated sulfones is enabled by visible-light photoredox catalysis. A wide range of readily available mono-, di-, and trifluoromethyl heteroaryl sulfones can thus be used as efficient radical fluoroalkylation reagents under mild conditions. This method not only describes a new synthetic application of fluorinated sulfones, but also provides a new route to fluoroalkyl radicals.
- Rong, Jian,Deng, Ling,Tan, Ping,Ni, Chuanfa,Gu, Yucheng,Hu, Jinbo
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supporting information
p. 2743 - 2747
(2016/02/26)
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- Trifluoromethylation of thiophenols and thiols with sodium trifluoromethanesulfinate and iodine pentoxide
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A selective and facile trifluoromethylation process for a wide range of thiophenols and thiols under metal free conditions has been developed using two simple and safe solids, sodium trifluoro-methanesulfinate and iodine pentoxide, via the radical process.
- Ma, Jing-Jing,Yi, Wen-Bin,Lu, Guo-Ping,Cai, Chun
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p. 417 - 421
(2016/02/03)
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- Copper-catalyzed synthesis of aryl and alkyl trifluoromethyl sulfides using CF3SiMe3and Na2S2O3as -SCF3source
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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.
- Zhong, Wei,Liu, Xiaoming
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supporting information
p. 4909 - 4911
(2014/12/10)
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- A mild and fast photocatalytic trifluoromethylation of thiols in batch and continuous-flow
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S-CF3 bonds are important structural motifs in various pharmaceutical and agrochemical compounds. However, their preparation remains a major challenge in synthetic organic chemistry. Here, we report the development of a mild and fast photocatalytic trifluoromethylation of thiols. The combination of commercially available Ru(bpy)3Cl2, visible light and inexpensive CF3I gas proved to be an efficient method for the direct trifluoromethylation of thiols. The protocol is demonstrated on a wide range of aromatic, hetero-aromatic and aliphatic substrates in both batch and continuous microflow (32 examples, 52-98% yield). Process intensification through continuous microflow application resulted in a 15-fold increase in production rate (0.25 mmol min-1) due to improved gas-liquid mass transfer, enhanced irradiation as well as convenient handling of the gaseous CF3 source. Furthermore, the efficiency of the flow process allowed to reduce the amount of CF3I (1.1 equivalent) to reach full conversion. This journal is
- Straathof, Natan J. W.,Tegelbeckers, Bart J. P.,Hessel, Volker,Wang, Xiao,Nol, Timothy
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p. 4768 - 4773
(2015/01/09)
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- An air-stable copper reagent for nucleophilic trifluoromethylthiolation of aryl halides
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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
- Weng, Zhiqiang,He, Weiming,Chen, Chaohuang,Lee, Richmond,Tan, Davin,Lai, Zhiping,Kong, Dedao,Yuan, Yaofeng,Huang, Kuo-Wei
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supporting information
p. 1548 - 1552
(2013/03/13)
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- Convenient synthesis and isolation of trifluoromethylthio-substituted building blocks
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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.
- Harsányi, Antal,Dorkó, éva,Csapó, ágnes,Bakó, Tibor,Peltz, Csaba,Rábai, József
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experimental part
p. 1241 - 1246
(2011/11/12)
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- Nucleophilic perfluoroalkylation of aldehydes, ketones, imines, disulfides, and diselenides
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Using a procedure analogous to that developed for nucleophilic trifluoromethylation, the perfluoroalkyl anion reagents created by mixing C 2F5I and n-C4F9I with tetrakis(dimethylamino)ethylene (TDAE) were effective in their nucleophilic reactions with aldehydes, ketones, imines, disulfides, and diselenides. Irradiation proved beneficial in the aldehyde and ketone reactions.
- Pooput, Chaya,Dolbier Jr., William R.,Medebielle, Maurice
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p. 3564 - 3568
(2007/10/03)
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- A New and Efficient Method for the Synthesis of Trifluoromethylthio- and Selenoethers
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(Equation presented) A new atom-economic procedure for preparation of trifluoromethyl thio- and selenoethers is reported, wherein both halves of aryl and alkyl disulfides and diselenides are able to be utilized with high efficiency.
- Pooput, Chaya,Medebielle, Maurice,Dolbier Jr., William R.
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p. 301 - 303
(2007/10/03)
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- A convenient synthesis of trifluoromethyl aryl sulfides
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Trifluoromethyl aryl sulfides are obtained in moderate/good yields by heating potassium trifluoroacetate and aryl disulfides in sulfolane. Copyright (C) 1996 Elsevier Science Ltd.
- Quiclet-Sire, Beatrice,Saicic, Radomir N.,Zard, Samir Z.
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p. 9057 - 9058
(2007/10/03)
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- THE INVENTION OF NEW RADICAL CHAIN REACTIONS. PART XIII. GENERATION AND REACTIVITY OF PERFLUOROALKYL RADICALS FROM THIOHYDROXAMIC ESTERS
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The perfluoro acid esters of N-hydroxypyridine 2-thione give perfluoroalkyl radicals on irradiation.Without any trap the radicals participate in a decarboxylative rearrangement to give 2-perfluoroalkylthiopyridines in excellent yield.In the presence of an appropriate trap, such as an electron rich olefin, adducts are formed in variable yield.
- Barton, Derek H. R.,Lacher, Brigitte,Zard, Samir Z.
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p. 2325 - 2328
(2007/10/02)
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- PREPARATION OF BROMODIFLUOROMETHYL SULFIDE AND ITS CONVERSION TO TRIFLUOROMETHYL SULFIDE
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Bromodifluoromethyl sulfides are prepared by the reaction of mercaptides with CF2BrX (x=Br,Cl).And treatment of bromodifluoromethyl sulfides with various inorganic fluorides produced trifluoromethyl sulfides.
- Suda, Minoru,Hino, Chiaki
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p. 1997 - 2000
(2007/10/02)
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