- Electrochemical Trifluoromethylation of Thiophenols with Sodium Trifluoromethanesulfinate
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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.
- Zhu, Xing-Xing,Wang, Huai-Qin,Li, Chen-Guang,Xu, Xiao-Lan,Xu, Jun,Dai, Jian-Jun,Xu, Hua-Jian
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supporting information
p. 16114 - 16120
(2021/02/03)
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- Trifluoromethyl Sulfoxides: Reagents for Metal-Free C?H Trifluoromethylthiolation
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Trifluoromethyl sulfoxides are a new class of trifluoromethylthiolating reagent. The sulfoxides engage in metal-free C?H trifluoromethylthiolation with a range of (hetero)arenes. The method is also applicable to the functionalization of important compound classes, such as ligand derivatives and polyaromatics, and in the late-stage trifluoromethylthiolation of medicines and agrochemicals. The isolation and characterization of a sulfonium salt intermediate supports an interrupted Pummerer reaction mechanism.
- Carlton, C. Grace,McDouall, Joseph J. W.,Perry, Gregory J. P.,Procter, David J.,Tayu, Masanori,Wang, Dong
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supporting information
p. 15918 - 15922
(2020/07/20)
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- Perfluoroalkylation of Thiosulfonates: Synthesis of Perfluoroalkyl Sulfides
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A practical synthesis of perfluoroalkyl sulfides is described. The method employs stable and readily accessible thiosulfonates as new electrophiles with commercial nucleophilic perfluoroalkylating reagents. The mild reaction conditions allow access to a wide variety of both aryl- and alkyl-substituted perfluoroalkyl sulfides amenable to pharmaceutical development. Furthermore, the reaction operation is straightforward, odorless, does not produce toxic wastes, and, therefore should appeal to practitioners in industrial-scale productions.
- Luo, Ziwei,Yang, Xinkan,Tsui, Gavin Chit
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supporting information
p. 6155 - 6159
(2020/07/30)
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- One pot synthesis of trifluoromethyl aryl sulfoxides by trifluoromethylthiolation of arenes and subsequent oxidation with hydrogen peroxide
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Hydrogen peroxide was used for oxidation of various aryl trifluoromethyl sulfides. Trifluoroacetic acid was used as an activating solvent that enables non-catalyzed oxidation and increases selectivity for sulfoxide formation. As shown by oxidation of thianthrene TFA enhances electrophilic character of the oxidant and further oxidation of sulfoxide group is blocked. We have joined trifluoromethylthiolation of arenes using a modified Billard reagent (p-ClPhNHSCF3) with oxidation of aryl trifluoromethyl sulfides using 1.2 equiv. of 30% aqueous hydrogen peroxide and this one-pot process has superior yields than would have been obtained in a two step process.
- Horvat, Monika,Iskra, Jernej,Jereb, Marjan,Kodri?, Gregor
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p. 34534 - 34540
(2020/10/12)
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- Visible-Light-Mediated Synthesis of Trifluoromethylthiolated Arenes
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The visible-light-mediated synthesis of trifluoromethylthiolated arenes in the presence of ruthenium-based photocatayst under mild reaction conditions is reported. The trifluoromethylthiolated arenes are obtained using the shelf-stable reagent trifluoromethyl toluenethiosulfonate at room temperature. The reaction proceeds selectively and does not require the presence of any additive. A mechanism is proposed based on the obtained results of EPR as well as luminescence.
- Ghiazza, Clément,Monnereau, Cyrille,Khrouz, Lhoussain,Billard, Thierry,Tlili, Anis
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supporting information
p. 2865 - 2870
(2019/07/09)
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- Transition-Metal-Free ipso-Trifluoromethylthiolation of Lithium Aryl Boronates
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A transition-metal-free direct trifluoromethylthiolation of the ipso-carbon of lithium aryl boronates with trifluoromethanesulfenate under mild conditions was described. In addition, late-stage site-selective C-H borylation/trifluoromethylation and C-Cl b
- Shen, Feng,Zheng, Hanliang,Xue, Xiao-Song,Lu, Long,Shen, Qilong
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p. 6347 - 6351
(2019/08/20)
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- Electrochemical ipso-Thiocyanation of Arylboron Compounds
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An operationally simple electrochemical method for the transition-metal-free ipso-thiocyanation of arylboronic acids and aryl trifluoroborates has been developed. The SCN electrophile is generated in situ by anodic oxidation of thiocyanate anions, which avoids formation of salt waste and prevents unwanted side reactions arising from chemical oxidants. The reaction proceeds regiospecifically, and the scope extends to non-activated aromatic systems. (Figure presented.).
- Dyga, Marco,Hayrapetyan, Davit,Rit, Raja K.,Goo?en, Lukas J.
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p. 3548 - 3553
(2019/04/26)
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- Copper(I)-promoted trifluoromethylthiolation of arenediazonium salts with AgSCF3
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An efficient method for trifluoromethylthiolation of arenediazonium salts has been developed in mild conditions with a stable and convenient AgSCF3. It provides a straightforward and convenient way for the synthesis of trifluoromethylthiolated compound from diazonium salts in moderate to good yields.
- Zheng, Changge,Liu, Yang,Hong, Jianquan,Huang, Shuai,Zhang, Wei,Yang, Yupeng,Fang, Ge
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supporting information
p. 1404 - 1407
(2019/05/01)
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- A process for converting substituted phenyl diazonium salts into [(trifluoromethyl)thio]benzene
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The invention discloses a synthetic method of [(trifluoromethyl)thio]benzene compounds, particularly a method for converting substituted phenyl diazonium salts into [(trifluoromethyl)thio]benzene. Themethod comprises the following steps: under white light
- -
-
Paragraph 0046-0053
(2019/12/02)
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- Lewis Base/Bronsted Acid Dual-Catalytic C-H Sulfenylation of Aromatics
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A Lewis base/Bronsted acid catalyzed aromatic sulfenylation is reported. These studies demonstrated that the incorporation of electron-rich sulfenyl groups proceeded in the absence of a Lewis base, with kinetic studies indicating an autocatalytic mechanism. The incorporation of electron-poor sulfenyl groups demonstrated little autocatalysis necessitating the use of a Lewis base. This method proved amenable to diverse arenes and heterocycles and was effective in the context of the late-stage functionalization of biologically active small molecules.
- Nalbandian, Christopher J.,Brown, Zachary E.,Alvarez, Erik,Gustafson, Jeffrey L.
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supporting information
p. 3211 - 3214
(2018/06/11)
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- Tf2O-Promoted Trifluoromethythiolation of Various Arenes Using NaSO2CF3
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A sulfonic anhydride-promoted direct trifluoromethylthiolation using NaSO2CF3 has been developed. The simple and practical strategy enabled the direct introduction of SCF3 moiety into unexplored arene scaffolds under reductant- and metal-free condition at room temperature. (Figure presented.).
- Liu, Jie,Zhao, Xiaochun,Jiang, Lvqi,Yi, Wenbin
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supporting information
p. 4012 - 4016
(2018/09/20)
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- Diversification of Trifluoromethylthiolation of Aromatic Molecules with Derivatives of Trifluoromethanesulfenamide
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Trifluoromethylthiolation of aromatic compounds with different electrophilic reagents of the type ArNHSCF3 was studied in the presence of triflic acid as an activator. The effect of the reagent structure on the reactivity was studied with three different reagents: PhNHSCF3 (H/SCF3, 1a), 4-ClC6H4NHSCF3 (Cl/SCF3, 1b) and C6F5NHSCF3 (F5/SCF3, 1c). p-Chloro substituted reagent 1b was more stable than the unsubstituted 1a and was the most effective because it could not react by trifluoromethylthiolation of itself. This reaction was the most important side reaction of 1a. The pentafluoro derivative 1c was less reactive. Solvent played an important role in the transformation and, depending on the substrate, dichloromethane, hexane or trifluoroacetic acid gave the best yield of various trifluoromethylthiolated aromatic molecules (63–98 %).
- Horvat, Monika,Jereb, Marjan,Iskra, Jernej
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p. 3837 - 3843
(2018/07/31)
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- Metal-free trifluoromethylthiolation of arenediazonium salts with Me4NSCF3
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A metal-free entry to the pharmaceutically meaningful substrate class of trifluoromethyl thioethers has been developed starting from widely available arenediazonium salts and commercially available Me4N+SCF3?. This reaction proceeds within one hour at 0 °C and is applicable to a wide range of functionalized substrates.
- Bertoli, Giulia,Exner, Benjamin,Evers, Mathies V.,Tschulik, Kristina,Goo?en, Lukas J.
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p. 132 - 136
(2018/04/05)
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- Preparation of Electrophilic Trifluromethylthio Reagents from Nucleophilic Tetramethylammonium Trifluoromethylthiolate
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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.).
- Kovács, Szabolcs,Bayarmagnai, Bilguun,Goossen, Lukas J.
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supporting information
p. 250 - 254
(2017/02/05)
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- Cu-mediated oxidative trifluoromethylthiolation of arylboronic acids with (bpy)CuSCF3
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An efficient trifluoromethylthiolation reaction of arylboronic acids with (bpy)CuSCF3in the presence of oxygen at room temperature is described. This method produces a variety of aryl trifluoromethylthioether derivatives in good to high yield. The mechanism of this trifluoromethylthiolation is discussed as well.
- Zhao, Mingzhu,Zhao, Xiaoming,Zheng, Purui,Tian, Yawei
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- Radical Aromatic Trifluoromethylthiolation: Photoredox Catalysis vs. Base Mediation
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Trifluoromethyl aryl sulfides (Ar-SCF3) constitute highly attractive building blocks due to their exceptional lipophilicity and chemical properties. Related protocols of radical aromatic trifluoro-methylthiolation of arenediazonium salts were developed that are based on the facile generation of intermediate aryl radicals. Their reactions with commercial F3CS-SCF3 under very mild conditions afforded a diverse set of Ar-SCF3 (3]Cl2} with the weak base-mediated dark reaction documented higher synthetic efficiency of the former but higher operational simplicity of the latter strategy.
- Koziakov, Denis,Majek, Michal,Jacobi von Wangelin, Axel
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supporting information
p. 6722 - 6725
(2017/12/07)
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- Silver-catalyzed fluoroalkylation of thiols using fluoroalkanesulfinates
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A practical sliver-catalyzed fluoroalkylation of aryl-, heteroaryl- and alkylthiols has been developed. The reaction has a good functional-group tolerance and excellent selectivity. A variety of stable and solid fluoroalkanesulfinates including di- and perfluoroalkanesulfinates can be employed. This methodology provides a straightforward and streamlined access to perfluoroalkylthiolated organic molecules. [Figure presented]
- Ma, Jing-jing,Liu, Qi-ran,Lu, Guo-ping,Yi, Wen-bin
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supporting information
p. 113 - 117
(2017/01/03)
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- Fluorodecarboxylation: Synthesis of aryl trifluoromethyl ethers (ArOCF3) and thioethers (ArSCF3)
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Fluorodecarboxylation of aryloxydifluoroacetic acid (ArOCF2CO2H) and arylmercaptodifluoroacetic acid (ArSCF2CO2H) towards ArXCF3 (X = O, S) using silver (I) salts in the presence of Selectfluor in a biphasic system with trifluoroacetic acid additive is discussed.
- Krishanmoorthy, Sankarganesh,Schnell, Simon D.,Dang, Huong,Fu, Fang,Prakash, G.K. Surya
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p. 130 - 135
(2017/09/06)
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- Triphenylphosphine-Mediated Deoxygenative Reduction of CF3SO2Na and Its Application for Trifluoromethylthiolation of Aryl Iodides
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We report herein a practical method for taming Langlois' reagent CF3SO2Na to generate CuSCF3 by a triphenylphospine-mediated deoxygenative reduction process. This chemistry highlights a novel utilization of the inherent CF3S skeleton of Langlois' reagent as a CF3S feedstock under mild conditions. The CuSCF3 intermediate generated by this protocol can react with a wide array of supporting ligands to furnish several air-stable [LCu(SCF3)] complexes as valuable trifluoromethylthiolating agents. In addition, the CuSCF3 intermediate can be directly employed for the trifluoromethylthiolation of (hetero)aryl iodides with operational simplicity and atomic efficiency. Efficient synthesis! A low cost method for the generation of CuSCF3 by a triphenylphospine-mediated deoxygenative reduction of Langlois' reagent (CF3SO2Na) has been developed (see scheme). This method can be applied for the convenient synthesis of a wide array of ligated and air-stable CuSCF3 complexes. Additionally, the CuSCF3 complexes generated in situ by this protocol were found to trifluoromethylthiolate (hetero)aryl iodides with high efficiency.
- Yang, Yi,Xu, Long,Yu, Siqi,Liu, Xiaoqiang,Zhang, Yu,Vicic, David A.
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supporting information
p. 858 - 863
(2016/01/16)
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- Metal-free radical thiolations mediated by very weak bases
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Aromatic thioethers and analogous heavier chalcogenides were prepared by reaction of arene-diazonium salts with disulfides in the presence of the cheap and weak base NaOAc. The mild and practical reaction conditions (equimolar reagents, DMSO, r.t., 8 h) tolerate various functional groups (e.g. Br, Cl, NO2, CO2R, OH, SCF3, furans). Mechanistic studies indicate the operation of a radical aromatic substitution mechanism via aryl, acetyloxyl, thiyl, and dimsyl radicals.
- Koziakov, Denis,Majek, Michal,Jacobi Von Wangelin, Axel
-
supporting information
p. 11347 - 11352
(2016/12/16)
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- Copper-Mediated Oxidative Trifluoromethylthiolation of Potassium Aryltrifluoroborates with Elemental Sulfur and Ruppert-Prakash Reagent
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A facile procedure for the copper-mediated oxidative trifluoromethylthiolation of potassium aryl- and heteroaryltrifluoroborates with Ruppert-Prakash reagent and elemental sulfur is presented. Aryl trifluoromethyl thioethers can be prepared in good to mod
- Dubbaka, Srinivas Reddy,Atthunuri, Azmi Reddy,Prakash, Koraboina Chandra,Rangabashyam, Prabhu,Gadde, Satyanarayana,Kothandaraman, Rajesh
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supporting information
p. 1246 - 1252
(2016/05/09)
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- Sandmeyer-Type Trifluoromethylthiolation and Trifluoromethylselenolation of (Hetero)Aromatic Amines Catalyzed by Copper
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Aromatic and heteroaromatic diazonium salts were efficiently converted into the corresponding trifluoromethylthio- or selenoethers by reaction with Me4NSCF3 or Me4NSeCF3, respectively, in the presence of catalytic amounts of copper thiocyanate. These Sandmeyer-type reactions proceed within one hour at room temperature, are applicable to a wide range of functionalized molecules, and can optionally be combined with the diazotizations into one-pot protocols.
- Matheis, Christian,Wagner, Victoria,Goossen, Lukas J.
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supporting information
p. 79 - 82
(2016/01/25)
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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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- Fundamental studies and development of nickel-catalyzed trifluoromethylthiolation of aryl chlorides: Active catalytic species and key roles of ligand and traceless MeCN additive revealed
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A catalytic protocol to convert aryl and heteroaryl chlorides to the corresponding trifluoromethyl sulfides is reported herein. It relies on a relatively inexpensive Ni(cod)2/dppf (cod = 1,5-cyclooctadiene; dppf = 1,1′-bis(diphenylphosphino)ferrocene) catalyst system and the readily accessible coupling reagent (Me4N)SCF3. Our computational and experimental mechanistic data are consistent with a Ni(0)/Ni(II) cycle and inconsistent with Ni(I) as the reactive species. The relevant intermediates were prepared, characterized by X-ray crystallography, and tested for their catalytic competence. This revealed that a monomeric tricoordinate Ni(I) complex is favored for dppf and Cl whose role was unambiguously assigned as being an off-cycle catalyst deactivation product. Only bidentate ligands with wide bite angles (e.g., dppf) are effective. These bulky ligands render the catalyst resting state as [(P-P)Ni(cod)]. The latter is more reactive than Ni(P-P)2, which was found to be the resting state for ligands with smaller bite angles and suffers from an initial high-energy dissociation of one ligand prior to oxidative addition, rendering the system unreactive. The key to effective catalysis is hence the presence of a labile auxiliary ligand in the catalyst resting state. For more challenging substrates, high conversions were achieved via the employment of MeCN as a traceless additive. Mechanistic data suggest that its beneficial role lies in decreasing the energetic span, therefore accelerating product formation. Finally, the methodology has been applied to synthetic targets of pharmaceutical relevance.
- Yin, Guoyin,Kalvet, Indrek,Englert, Ulli,Schoenebeck, Franziska
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supporting information
p. 4164 - 4172
(2015/04/14)
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- Iron-Catalyzed Decarboxylation of Trifluoroacetate and Its Application to the Synthesis of Trifluoromethyl Thioethers
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Nucleophilic CF3 has been generated by decarboxylation of potassium trifluoroacetate, arguably the most easy-to-handle, inexpensive, and sustainable source of trifluoromethyl groups. Simple iron(II) chloride catalyzes the decarboxylation as well as a subsequent trifluoromethylation of organothiocyanates, resulting in a straightforward synthesis of trifluoromethyl thioethers. The KCN byproduct is absorbed by iron(II) with formation of nontoxic potassium hexacyanoferrate. An analogous trifluoromethylation of aldehydes with trifluoroacetate underlines the synthetic potential of such iron-catalyzed decarboxylative trifluoromethylations.
- Exner, Benjamin,Bayarmagnai, Bilguun,Jia, Fan,Goossen, Lukas J.
-
supporting information
p. 17220 - 17223
(2016/01/25)
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- Copper-Catalyzed Trifluoromethylthiolation of Di(hetero)aryl-λ3-iodanes: Mechanistic Insight and Application to Synthesis of (Hetero)Aryl Trifluoromethyl Sulfides
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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.
- Saravanan, Perumal,Anbarasan, Pazhamalai
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supporting information
p. 3521 - 3528
(2016/01/25)
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- 18F-Labeling of Aryl-SCF3, -OCF3 and -OCHF2 with [18F]Fluoride
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We report that halogenophilic silver(I) triflate permits halogen exchange (halex) nucleophilic 18F-fluorination of aryl-OCHFCl, -OCF2Br and -SCF2Br precursors under mild conditions. This AgI-mediated process allows for the first time access to a range of 18F-labeled aryl-OCHF2, -OCF3 and -SCF3 derivatives, inclusive of [18F]riluzole. The 18F-labeling of these medicinally important motifs expands the radiochemical space available for PET applications. A halogen exchange (halex) 18F-fluorination process offers access for the first time to 18F-labeled arylOCF3, arylOCHF2 and arylSCF3, three motifs of established medicinal importance in PET radiotracers. The use of silver(I) triflate is critical to permit 18F-labeling under mild conditions.
- Khotavivattana, Tanatorn,Verhoog, Stefan,Tredwell, Matthew,Pfeifer, Lukas,Calderwood, Samuel,Wheelhouse, Katherine,Leecollier, Thomas,Gouverneur, Vronique
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p. 9991 - 9995
(2015/08/19)
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- Synthesis of Aryl Tri- and Difluoromethyl Thioethers via a C H-Thiocyanation/Fluoroalkylation Cascade
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An AlCl3-catalyzed C H thiocyanation was discovered and combined with a Langlois-type trifluoromethylation to afford aryl trifluoromethyl thioethers directly from arenes, N-thiocyanatosuccinimide (NTS) and Ruppert-Prakash reagent. An analogous combination with a copper-mediated difluoromethylation gives access to aryl difluoromethyl thioethers. Both processes proceed with exceptional regioselectivity for the most electron-rich, sterically least hindered position of the arene. The sulfur and fluoroalkyl groups originate from different sources, so that the use of expensive, preformed fluoroalkylthiolation reagents is avoided. Perfectly formed: An AlCl3-catalyzed C H thiocyanation was combined with a Langlois-type trifluoromethylation to afford aryl trifluoromethyl thioethers directly from arenes, N-thiocyanatosuccinimide, and TMS-CF3 (see scheme). An analogous combination of the thiocyanation with a copper-mediated difluoromethylation gives access to aryl difluoromethyl thioethers. The sulfur and fluoroalkyl groups originate from different sources, so that preformed fluoroalkylthiolation reagents are avoided.
- Jouvin, Kévin,Matheis, Christian,Goossen, Lukas J.
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supporting information
p. 14324 - 14327
(2015/10/05)
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- Mild and Soft Catalyzed Trifluoromethylthiolation of Boronic Acids: The Crucial Role of Water
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The most reactive 2nd generation of trifluoromethanesulfenamides undergoes a copper-catalyzed cross-coupling reaction with boronic acids to afford CF3S-molecules. Contrary to the previous methods in the literature, no base addition, no heating, and no large excess of reagents are required to obtain good results. Furthermore, a crucial role of a small amount of water to favor this reaction has been demonstrated. This constitutes the mildest described conditions for such a reaction.
- Glenadel, Quentin,Alazet, Sébastien,Tlili, Anis,Billard, Thierry
-
supporting information
p. 14694 - 14698
(2015/10/19)
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- Structure-reactivity relationship of trifluoromethanesulfenates: Discovery of an electrophilic trifluoromethylthiolating reagent
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A family of electrophilic trifluoromethanesulfenates was prepared. Structure-reactivity relationship studies showed that the substituted groups on the aryl ring of the trifluoromethylthiolating reagent did not have an obvious influence on their reactivities. A simplified electrophilic trifluoromethylthiolating reagent 1c was then identified that can react with a wide range of nucleophiles such as Grignard reagents, arylboronic acids, alkynes, indoles, β-ketoesters, oxindoles, and sodium sulfinates under mild reaction conditions. A variety of functional groups were tolerated under these conditions.
- Shao, Xinxin,Xu, Chunfa,Lu, Long,Shen, Qilong
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p. 3012 - 3021
(2015/03/30)
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- Electrophilic aromatic trifluoromethylthiolation with the second generation of trifluoromethanesulfenamide
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Direct trifluoromethylthiolation of various aromatic and heteroaromatic compounds, variously substituted, can be performed with the second generation of trifluoromethanesulfenamide via a 'Friedel-Crafts-like reaction'. This reaction requires mild conditions with a catalytic amount of protic or Lewis acid. Good results have been obtained, even with aromatic compounds bearing deactivating substituents.
- Alazet, Sébastien,Billard, Thierry
-
supporting information
p. 76 - 78
(2015/02/02)
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- Electrophilic aromatic trifluoromethylthiolation with the second generation of trifluoromethanesulfenamide
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Direct trifluoromethylthiolation of various aromatic and heteroaromatic compounds, variously substituted, can be performed with the second generation of trifluoromethanesulfenamide via a 'Friedel-Crafts-like reaction'. This reaction requires mild conditions with a catalytic amount of protic or Lewis acid. Good results have been obtained, even with aromatic compounds bearing deactivating substituents.
- Alazet, Sbastien,Billard, Thierry
-
supporting information
(2015/02/18)
-
- 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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- 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
-
supporting information
p. 4909 - 4911
(2014/12/10)
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- One-pot sandmeyer trifluoromethylation and trifluoromethylthiolation
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Practical one-pot procedures were developed for both Sandmeyer-type trifluoromethylations and trifluoromethylthiolations. Starting from broadly available (hetero)aromatic amines, various benzotrifluorides were synthesized in high yields via in situ diazotization and copper-mediated trifluoromethylation using the inexpensive Ruppert-Prakash trifluoromethylating reagent. In the presence of sodium thiocyanate as a sulfur source, aryl trifluoromethyl thioethers are exclusively formed.
- Bayarmagnai, Bilguun,Matheis, Christian,Risto, Eugen,Goossen, Lukas J.
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supporting information
p. 2343 - 2348
(2014/07/21)
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- Sandmeyer trifluoromethylthiolation of arenediazonium salts with sodium thiocyanate and Ruppert-Prakash reagent
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In the presence of copper thiocyanate, sodium thiocyanate and the inexpensive, easy-to-use trifluoromethylating reagent Me3Si-CF 3, diazonium salts are smoothly converted into the corresponding aryl trifluoromethyl thioethers. Combin
- Danoun, Gregory,Bayarmagnai, Bilguun,Gruenberg, Matthias F.,Goossen, Lukas J.
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p. 1312 - 1316
(2014/03/21)
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- Direct catalytic trifluoromethylthiolation of boronic acids and alkynes employing electrophilic shelf-stable N-(trifluoromethylthio)phthalimide
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A new and safe method for the synthesis of N-(trifluoromethylthio) phthalimide, a convenient and shelf-stable reagent for the direct trifluoromethylthiolation, has been developed. N-(Trifluoromethylthio) phthalimide can be used as an electrophilic source of F3CS + and reacts readily with boronic acids and alkynes under copper catalysis. The utility of CF3S-containing molecules as biologically active agents, the mild reaction conditions employed, and the high tolerance of functional groups demonstrate the potential of this new methodology to be widely applied in organic synthesis as well as industrial pharmaceutical and agrochemical research and development. Shelf life: A new and safe method for the synthesis of N-(trifluoromethylthio)phthalimide has been developed. It serves as a convenient and shelf-stable reagent for the direct copper-catalyzed trifluoromethylthiolation of readily available boronic acids and alkynes. Copyright
- Pluta, Roman,Nikolaienko, Pavlo,Rueping, Magnus
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supporting information
p. 1650 - 1653
(2014/03/21)
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- An electrophilic hypervalent iodine reagent for trifluoromethylthiolation
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Sulfur and friends: A new electrophilic hypervalent iodine reagent 1 has been developed for direct trifluoromethylthiolation. A variety of nucleophiles, including β-ketoesters, aldehydes, amides, aryl or vinyl boronic acids, and alkynes, reacted with 1 under mild conditions to give the corresponding trifluoromethylthiolated compounds in good to excellent yields.
- Shao, Xinxin,Wang, Xueqiang,Yang, Tao,Lu, Long,Shen, Qilong
-
supporting information
p. 3457 - 3460
(2013/04/24)
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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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- Nickel-catalyzed synthesis of aryl trifluoromethyl sulfides at room temperature
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Inexpensive nickel-bipyridine complexes were found to be active for the trifluoromethylthiolation of aryl iodides and aryl bromides at room temperature using the convenient [NMe4][SCF3] reagent.
- Zhang, Cheng-Pan,Vicic, David A.
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supporting information; experimental part
p. 183 - 185
(2012/03/07)
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- Electrophilic trifluoromethanesulfanylation of organometallic species with trifluoromethanesulfanamides
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It's so easy. Direct trifluoromethanesulfanylation reactions remain difficult to perform because of the lack of reagents that are stable and easy to handle. Trifluoromethanesulfanamides are reagents which, in combination with readily available Grignard re
- Baert, Francois,Colomb, Julie,Billard, Thierry
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supporting information
p. 10382 - 10385,4
(2012/12/11)
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- Oxidative trifluoromethylthiolations of aryl boronic acids using a copper/O2-based protocol
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All you need is air: A new protocol has been developed which can mediate the coupling of aryl and vinyl boronic acids at room temperature in high yields (see scheme, dtbpy=4,4'-di-tert-butyl-2,2'-bipyridine). The reactions take place using simple copper(II) salts under aerobic conditions and do not require the use of expensive silver oxidants.
- Zhang, Cheng-Pan,Vicic, David A.
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supporting information; experimental part
p. 1756 - 1758
(2012/08/28)
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- Copper-catalyzed oxidative trifluoromethylthiolation of aryl boronic acids with TMSCF3 and elemental sulfur
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Fluorinated functionality: The copper-catalyzed oxidative trifluoromethylthiolation of aryl boronic acids with TMSCF3 and elemental sulfur at room temperature is described for the first time. This reaction provides a concise and efficient method for the synthesis of aryl trifluoromethyl thioethers (ArSCF3) under mild conditions. Phen=Phenanthroline. Copyright
- Chen, Chao,Xie, Yan,Chu, Lingling,Wang, Ruo-Wen,Zhang, Xingang,Qing, Feng-Ling
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supporting information; experimental part
p. 2492 - 2495
(2012/05/20)
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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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- Selective oxidation and chlorination of trifluoromethylsulfide using trichloroisocyanuric acid in ionic liquid
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A route to chemoselective oxidation and chlorination of aryltrifluoromethylsulfide using trichloroisocyanuric acid (TCCA) in ionic liquid, an efficiently O-methylation reaction and a reduction of nitro- to amido- in excellent yields have been developed.
- Tang, Ri-Yuan,Zhong, Ping,Lin, Qiu-Lian
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p. 636 - 640
(2008/01/06)
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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 INTRODUCTION OF SCF3 INTO AROMATIC SUBSTRATES USING CuSCF3 AND ALUMINA-SUPPORTED CuSCF3
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Trifluoromethylthiocopper(I) has been readily prepared from the silver analogue, using a metathetical reaction with copper(I) bromide.Homogeneous CuSCF3 and the supported reagent CuSCF3-alumina have been compared in their reactivity towards aryl iodides, in order to form trifluoromethylaryl sulphides in good yields.
- Clark, James H.,Craig, W. Jones,Kybett, Adrian P.,McClinton, Martin A.,Miller, Jack M.,et al.
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p. 249 - 255
(2007/10/02)
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- Chemistry of Halogenoperfluoroalkanes> Synthesis of Fluorinated Ethers and Thioethers via Radical or Anionic Intermediates
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Condensation of bromotrifluoromethane with potassium thiophenoxides in DMF is performed under pressure (2-3 atm) in a glass apparatus.Inhibition by nitrobenzene shows that a SRN1 mechanism is involved in the formation of aryl trifluoromethyl sulfides.Dichlorodifluoromethane itself reacts through a similar process to give aryl chlorodifluoromethyl sulfides.Condensation of 1,1,2-trichlorotrifluoroethane with potassium thiophenoxide or phenoxide occurs even in the presence of nitrobenzene.The formation of aryl 2,2-dichloro-1,1,2-trifluoroethyl sulfides or ethers can be explained by a chain carbanionic mechanism.
- Wakselman, Claude,Tordeux, Marc
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p. 4047 - 4051
(2007/10/02)
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- SRN1 Substitutions of Halogenoperfluoroalkanes (CF3Br or CF2Cl2) under Pressure
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Radical chain fluoroalkylation of arenethiolates by CF3Br or CF2Cl2, performed under slight pressure in a glass apparatus, gives aryl polyfluoromethyl sulphides.
- Wakselman, Claude,Tordeux, Marc
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p. 793 - 794
(2007/10/02)
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- Phase-Transfer Catalysed Ion-Radical Perfluoroalkylation of Thiols
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It has been shown that under conditions of phase-transfer catalysis under UV-irradiation perfluoroalkyl iodides react with aliphatic and aromatic thiols in the water-organic solvent media to form alkyl or aryl perfluoroalkyl sulfides in 60-80 percent yields.
- Popov, V. I.,Boiko, V. N.,Yagupolskii, L. M.
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p. 365 - 370
(2007/10/02)
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