- 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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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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- 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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- 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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- 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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- O-Trifluoromethylation of Phenols: Access to Aryl Trifluoromethyl Ethers by O-Carboxydifluoromethylation and Decarboxylative Fluorination
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A new strategy for the synthesis of aryl trifluoromethyl ethers (ArOCF3) by combining O-carboxydifluoromethylation of phenols and subsequent decarboxylative fluorination is reported. This protocol allows easy construction of functionalized trifluoromethoxybenzenes and trifluoromethylthiolated arenes (ArSCF3) in moderate to good yields. Moreover, it utilizes accessible and inexpensive reagents sodium bromodifluoroacetate and SelectFluor II and, thus, is practical for O-trifluoromethylation of phenols. The potential application of this method is demonstrated with the preparation of a plant-growth regulator, Flurprimidol.
- Zhou, Min,Ni, Chuanfa,He, Zhengbiao,Hu, Jinbo
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supporting information
p. 3754 - 3757
(2016/08/16)
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- Trifluoromethylthiolation of Unsymmetrical λ3-Iodane Derivatives: Additive-Free, Selective and Scalable Introduction of the SCF3 Group
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The reaction of copper trifluoromethyl sulfide with diaryliodonium salts provides a straightforward pathway for the synthesis of aryl trifluoromethyl thioethers under mild reaction conditions and within short reaction times. High chemoselectivity was achieved by using mesityl as a leaving group. A large range of novel [(het)aryl](mesityl)iodonium salts underwent this reaction under the optimized conditions to give the desired products in moderate to good yields.
- Nikolaienko, Pavlo,Yildiz, Tülay,Rueping, Magnus
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p. 1091 - 1094
(2016/03/05)
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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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- 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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- 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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- S-Trifluoromethylation of Thiols by Hypervalent Iodine Reagents: A Joint Experimental and Computational Study
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The radical trifluoromethylation of thiophenol in condensed phase applying reagent 1 (3,3-dimethyl-1-(trifluoromethyl)-1λ3,2-benziodoxol) has been examined by both theoretical and experimental methodologies. On the basis of ab initio molecular
- Sala, Oliver,Santschi, Nico,Jungen, Stefan,Lüthi, Hans Peter,Iannuzzi, Marcella,Hauser, Nicole,Togni, Antonio
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supporting information
p. 1704 - 1713
(2016/02/20)
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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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- 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.
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p. 17220 - 17223
(2016/01/25)
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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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- 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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- 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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- 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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- Electronic nature of perfluoroalkylthio-, perfluoroalkylseleno-, and perfluoroalkyltelluro-containing substituents
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The ? constants of perfluoroalkylthio, perfluoroalkylseleno, perfluoroalkyltelluro, and perfluoroalkylsulfonyl groups were determined by the 19F NMR method.It was shown that the perfluoro-tert-butylsulfonyl group is the most electron-withdrawing of all the known stable substituents.The dipole moments of aryl perfluoroalkyl sulfides and sulfones were determined.
- Kondratenko, N. V.,Popov, V. I.,Kolomeitsev, A. A.,Saenko, E. P.,Prezhdo, V. V.,et al.
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p. 1049 - 1054
(2007/10/02)
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