- 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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- Deoxygenative trifluoromethylthiolation of carboxylic acids
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Here we describe a deoxygenative trifluoromethylthiolation method that yields trifluoromethyl thioesters from readily available carboxylic acids. The method is built upon an "umpolung" strategy where triphenylphosphine is used to first activate an electro
- Mao, Runze,Bera, Srikrishna,Cheseaux, Alexis,Hu, Xile
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Read Online
- Gold (I/III)-Catalyzed Trifluoromethylthiolation and Trifluoromethylselenolation of Organohalides
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The first C?SCF3/SeCF3 cross-coupling reactions using gold redox catalysis [(MeDalphos)AuCl], AgSCF3 or Me4NSeCF3, and organohalides as substrates are reported. The new methodology enables a one-stop shop synthesis of aryl/alkenyl/alkynyl trifluoromethylthio- and selenoethers with a broad substrate scope (>60 examples with up to 97 % isolated yield). The method is scalable, and its robustness is evidenced by the late-stage functionalization of various bioactive molecules, which makes this reaction an attractive alternative in the synthesis of trifluoromethylthio- and selenoethers for pharmaceutical and agrochemical research and development.
- Mudshinge, Sagar R.,Yang, Yuhao,Xu, Bo,Hammond, Gerald B.,Lu, Zhichao
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supporting information
(2022/02/10)
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- S-(Trifluoromethyl)Benzothioate (TFBT): A KF-Based Reagent for Nucleophilic Trifluoromethylthiolation
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S-(Trifluoromethyl)benzothioate (TFBT) has been developed as an inexpensive, bench-stable, and user-friendly trifluoromethylthiolation reagent, which can be easily synthesized by using KF as the only fluorine source. By using TFBT, trifluoromethylthiolates with various counterions can be readily obtained. The synthetic application of TFBT was demonstrated by trifluoromethylthiolation-halogenation of arynes, bis(trifluoromethylthiolation)–halogenation of 1,2-benzdiynes, nucleophilic substitution of alkyl halides, deoxytrifluoromethylthiolation of alcohols, and cross-coupling with aryl and vinyl boronic acids.
- Meng, Depei,Lyu, Yichong,Ni, Chuanfa,Zhou, Min,Li, Yang,Hu, Jinbo
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supporting information
(2022/02/17)
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- Transition-Metal-Free Synthesis of Aryl Trifluoromethyl Thioethers through Indirect Trifluoromethylthiolation of Sodium Arylsulfinate with TMSCF3
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Herein, we report an indirect trifluoromethylthiolation of sodium arylsulfinates. This transition-metal-free reaction significantly provides an environmentally friendly and practical synthetic method for aryl trifluoromethyl thioethers using commercial Ruppert-Prakash reagent TMSCF3. This approach is also a potential alternative to the current industrial production method owing to facile substrates, excellent functional group compatibility, and operational simplicity.
- Zheng, Changge,Jiang, Chao,Huang, Shuai,Zhao, Kui,Fu, Yingying,Ma, Mingyu,Hong, Jianquan
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p. 6982 - 6986
(2021/09/08)
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- Metal-Free Direct Trifluoromethylthiolation of Aromatic Compounds Using Triptycenyl Sulfide Catalyst
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Herein we report an efficient synthetic method for the electrophilic trifluoromethylthiolation of aromatic compounds. The key is to use triptycenyl sulfide (Trip-SMe) and TfOH to enhance the electrophilicity of SCF3 fragment through the formation of sulfonium intermediates. This method enables direct installation of an SCF3 group onto unactivated aromatics at room temperature, adopting a commercially available saccharin-based reagent. Preliminary DFT calculation was carried out to investigate the substitution effect on the catalytic activity.
- Kurose, Ryo,Nishii, Yuji,Miura, Masahiro
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supporting information
p. 2380 - 2385
(2021/04/05)
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- Preparation method of trifluoromethyl aryl thioether
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The invention discloses a preparation method of trifluoromethyl aryl thioether, and belongs to the field of chemicals for daily use in chemical industry. Aryl sulfinate and trifluoromethyl trimethyl silane are used as substrates, no transition metal catalyst is needed, and trifluoromethyl aryl thioether is obtained through reaction under the action of an additive, an oxidizing agent and alkali. The reaction can be carried out in a room-temperature environment, the reaction is green, simple and convenient, the reaction yield is as high as 55%, and a new approach of a trifluoromethylthiolation indirect method is provided in the field of fluorine chemistry; the obtained product has wide application in the fields of medicines, pesticides and materials.
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Paragraph 0027; 0036-0038; 0042-0060
(2021/02/20)
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- Metal-Free Trifluoromethylthiolation of Arylazo Sulfones
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A visible-light-driven protocol for the synthesis of aryl trifluoromethyl thioethers under photocatalyst- and metal-free conditions has been pursued. The procedure exploits the peculiar properties of arylazo sulfones (having electron-rich or electron-poor substituents on the (hetero)aromatic ring) as photochemical precursors of aryl radicals and S-trifluoromethyl arylsulfonothioates as easy-to-handle trifluoromethylthiolating agents.
- Li, Ankun,Li, Yuxuan,Liu, Junjie,Chen, Jingqi,Lu, Kui,Qiu, Di,Fagnoni, Maurizio,Protti, Stefano,Zhao, Xia
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p. 1292 - 1299
(2021/01/14)
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- Method for synthesizing trifluoromethylthio compound by using trifluoromethyl sulfinyl chloride
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The invention discloses a method for synthesizing a trifluoromethylthio compound by using trifluoromethyl sulfinyl chloride. The method comprises the following steps: taking alkyne/aromatic compoundsand the trifluoromethyl sulfinyl chloride as raw materials, taking N, N-dimethylformamide as a solvent, fully reacting at 90 +/-5 DEG C, cooling to room temperature after the reaction is finished, extracting, carrying out reduced pressure distillation, and carrying out column chromatography separation and purification on a reaction mixture so as to obtain the trifluoromethylthio compound. The method is simple and safe in process, high in reaction conversion rate, economical and practical in used raw materials, less in three wastes, environment-friendly, free of catalysts and reducing agents and low in cost.
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Paragraph 0042-0046
(2020/11/09)
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- Electrophilic Hypervalent Trifluoromethylthio-Iodine(III) Reagent
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Herein we report the design and synthesis of hypervalent trifluoromethylthio-iodine(III) reagent 1 and the elucidation of its structure by NMR spectroscopy and X-ray crystallography. The trifluoromethylthiolation reactions of 1 with various nucleophiles were explored, and this compound was found to be a versatile electrophilic reagent for the transfer of a trifluoromethylthio group (-SCF3). The hydrogen-bonding mode responsible for the activation of 1 by the solvent 1,1,1,3,3,3-hexafluoro-2-propanol was investigated both experimentally and computationally.
- Yang, Xiao-Guang,Zhang, Chi,Zheng, Ke
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supporting information
p. 2026 - 2031
(2020/03/24)
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- Method for synthesizing aromatic trifluoromethylthio compound
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The invention discloses a method for synthesizing an aromatic trifluoromethylthio compound. The method comprises the following steps: reacting sodium trifluoromethanesulfinate with Chlorodiphenyl phosphine at room temperature; after reacting for a period of time, sequentially adding an aniline compound and tert-butyl nitrite, fully reacting at 70 +/-5 DEG C by taking CuSO4 as a catalyst and acetonitrile as a solvent, cooling to room temperature after the reaction is finished, extracting, carrying out reduced pressure distillation, and carrying out column chromatography separation and purification on the reaction mixture to obtain the aromatic trifluoromethylthio compound. The method is simple and safe in process operation and high in reaction conversion rate, the used raw materials are economical and practical, few three wastes are generated, and no extra organic solvent needs to be treated.
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Paragraph 0036-0034
(2020/11/09)
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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
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Paragraph 0070-0077
(2019/12/02)
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- Method for producing substituted [(trifluoromethyl)thio]benzene from substituted aniline
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The invention discloses a synthetic method of [(trifluoromethyl)thio]benzene compounds, particularly a method for preparing substituted [(trifluoromethyl)thio]benzene from substituted aniline. The method comprises the following steps: adding aromatic amine, a catalyst, tert-butyl nitrite and p-toluenesulfonic acid hydrate into a solvent; stirring the mixture for at least 5 minutes at the room temperature of 20-25 DEG C; then adding S-trifluoromethyl-4-methoxybenzenesulfonyl sulfate, and uniformly stirring the mixture; reacting the mixture under white light irradiation at the room temperature of 20-25 DEG C; determining the reaction ending time through spotting detection; after the reaction is finished, adding water for extraction; performing separation to obtain a liquid organic phase; drying the liquid organic phase with anhydrous Na2SO4; then removing a solvent; and performing rapid separation with column chromatography to obtain a [(trifluoromethyl)thio]benzene compound. The preparation method is mild in reaction condition, free of high-temperature and high-pressure reaction, safe in reaction condition and suitable for large-scale production and development.
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Paragraph 0060-0067
(2019/12/02)
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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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- 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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p. 1404 - 1407
(2019/05/01)
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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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- 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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- 2-Diazo-1-phenyl-2-((trifluoromethyl)sulfonyl)ethan-1-one: Another Utility for Electrophilic Trifluoromethylthiolation Reactions
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2-Diazo-1-phenyl-2-((trifluoromethyl)sulfonyl)ethan-1-one (diazo-triflone) (2) is not only a building block but also a reagent. In this study, diazo-triflone, which was originally used for the synthesis of β-lactam triflones as a trifluoromethanesulfonyl
- Huang, Zhongyan,Okuyama, Kenta,Wang, Chen,Tokunaga, Etsuko,Li, Xiaorui,Shibata, Norio
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p. 188 - 191
(2016/07/11)
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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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- 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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- Nickel-catalyzed trifluoromethylthiolation of Csp2-O bonds
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While nickel catalysts have previously been shown to activate even the least reactive Csp2-O bonds, i.e. aryl ethers, in the context of C-C bond formation, little is known about the reactivity limits and molecular requirements for the introduction of valuable functional groups under homogeneous nickel catalysis. We identified that due to the high reactivity of Ni-catalysts, they are also prone to react with existing or installed functional groups, which ultimately causes catalyst deactivation. The scope of the Ni-catalyzed coupling protocol will therefore be dictated by the reactivity of the functional groups towards the catalyst. Herein, we showed that the application of computational tools allowed the identification of matching functional groups in terms of suitable leaving groups and tolerated functional groups. This allowed for the development of the first efficient protocol to trifluoromethylthiolate Csp2-O bonds, giving the mild and operationally simple C-SCF3 coupling of a range of aryl, vinyl triflates and nonaflates. The novel methodology was also applied to biologically active and pharmaceutical relevant targets, showcasing its robustness and wide applicability.
- Dürr, Alexander B.,Yin, Guoyin,Kalvet, Indrek,Napoly, Fran?ois,Schoenebeck, Franziska
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p. 1076 - 1081
(2016/02/05)
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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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- 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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- Trifluoromethylthiolation of aryl iodides and bromides enabled by a bench-stable and easy-to-recover dinuclear palladium(I) catalyst
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Abstract While palladium catalysis is ubiquitous in modern chemical research, the recovery of the active transition-metal complex under routine laboratory applications is frequently challenging. Described herein is the concept of alternative cross-coupling cycles with a more robust (air-, moisture-, and thermally-stable) dinuclear PdI complex, thus avoiding the handling of sensitive Pd0 species or ligands. Highly efficient C-SCF3 coupling of a range of aryl iodides and bromides was achieved, and the recovery of the PdI complex was accomplished via simple open-atmosphere column chromatography. Kinetic and computational data support the feasibility of dinuclear PdI catalysis. A novel SCF3-bridged PdI dimer was isolated, characterized by X-ray crystallography, and verified to be a competent catalytic intermediate. Pd double team: The cross-coupling enabled by an air-, moisture-, and thermally stable dinuclear PdI complex was explored. Highly efficient C-SCF3 coupling of a range of aryl iodides and bromides was achieved and the catalyst was recovered by simple column chromatography, thus highlighting its robustness and the possibility for catalyst recycling. Kinetic and computational data support the feasibility of dinuclear PdI catalysis.
- Yin, Guoyin,Kalvet, Indrek,Schoenebeck, Franziska
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supporting information
p. 6809 - 6813
(2015/06/08)
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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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supporting information
p. 9991 - 9995
(2015/08/19)
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- Reactions of allyl alcohols and boronic acids with trifluoromethanesulfonyl hypervalent iodonium ylide under copper-catalysis
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Trifluoromethylsulfinyl and trifluoromethylthio groups are both important substituents for pharmaceuticals, agrochemicals and functional materials. We herein report the trifluoromethylthiolation of allyl alcohols 2 with trifluoromethanesulfonyl hypervalent iodonium ylide 1 under copper catalysis to provide trifluoromethylsulfinyl compounds 3. Trifluoromethylthiolation of boronic acids 4 with 1 furnished trifluoromethylthio compounds 5.
- Arimori, Sadayuki,Takada, Masahiro,Shibata, Norio
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supporting information
p. 19456 - 19459
(2015/11/27)
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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
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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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- 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
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supporting information
p. 4909 - 4911
(2014/12/10)
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- Structural reevaluation of the electrophilic hypervalent iodine reagent for trifluoromethylthiolation supported by the crystalline sponge method for x-ray analysis
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Hypervalent iodine λ3-benziodoxoles are common electrophilic transfer reagents known for their enhanced stability compared to their non-cyclic analogues. Herein we present data showing that chlorobenziodoxole reacts with two different thiolate nucleophiles (thiocyanate and trifluoromethylthiolate), resulting in the formation of stable thioperoxy complexes rather than the expected benziodoxole derivatives. We further report a revised structure for the earlier described electrophilic trifluoromethylthiolation reagent (1), which was previously believed to contain the benziodoxole framework. Our findings, which are based on a combination of analytical techniques, including the recently introduced crystalline sponge method for X-ray analysis, unambiguously demonstrate that 1 is a thioperoxy compound both in solution and the solid state. Not-so-hypervalent iodine: Studies of several benziodoxole thiolate derivatives revealed that these species lack the hypervalent iodine motif, instead adopting a thioperoxide configuration. Crystallographic analysis of a liquid trifluoromethylthiolation reagent trapped inside a metal-organic framework provided direct structural proof for the observed phenomenon. These thioperoxide reagents were also shown to be reactive in electrophilic substitution reactions.
- Vinogradova, Ekaterina V.,Mueller, Peter,Buchwald, Stephen L.
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supporting information
p. 3125 - 3128
(2014/04/03)
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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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- Copper-mediated oxidative trifluoromethylthiolation of aryl boronic acids with CF3CO2Na and elemental sulfur
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A practical three-component copper-mediated oxidative trifluoromethylthiolation of aryl boronic acids with cheap and readily available sodium trifluoroacetate and elemental sulfur is reported. A variety of trifluoromethylthio-substituted aromatics are synthesized in moderate yields under mild reaction conditions.
- Zhai, Lijuan,Li, Yaming,Yin, Jun,Jin, Kun,Zhang, Rong,Fu, Xinmei,Duan, Chunying
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p. 10262 - 10266
(2013/11/19)
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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
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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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- 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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- 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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- Benchmark and Solvent-Free preparation of sulfonium salt based electrophilic trifluoromethylating reagents
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Here we describe work devoted to the one-pot preparation of electrophilic trifluoromethylating reagents. The first part describes a reappraisal of our earlier experimental conditions and leads to an improved protocol that avoids the use of solvent: and allows better yields. The second part carefully studies the behavior of biaryl substrates, whose structures can drive the reaction through the formation of original noncyclic or tricyclic dibenzothiophenium salts. New compounds were tested, in a standard reaction with aniline, for their trifluoromethylating power and revealed equivalent or improved reactivity relative to that of existing reagents. Furthermore, contrary to common knowledge, the presence of electron-donating methyl groups gave reagents with very high activity. Wiley-VCH Verlag GmbH & Co, KGaA.
- Mace, Yohan,Raymondeau, Benoit,Pradet, Charlotte,Blazejewski, Jean-Claude,Magnier, Emmanuel
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experimental part
p. 1390 - 1397
(2009/08/07)
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