- A “universal” catalyst for aerobic oxidations to synthesize (hetero)aromatic aldehydes, ketones, esters, acids, nitriles, and amides
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Functionalized (hetero)aromatic compounds are indispensable chemicals widely used in basic and applied sciences. Among these, especially aromatic aldehydes, ketones, carboxylic acids, esters, nitriles, and amides represent valuable fine and bulk chemicals, which are used in chemical, pharmaceutical, agrochemical, and material industries. For their synthesis, catalytic aerobic oxidation of alcohols constitutes a green, sustainable, and cost-effective process, which should ideally make use of active and selective 3D metals. Here, we report the preparation of graphitic layers encapsulated in Co-nanoparticles by pyrolysis of cobalt-piperazine-tartaric acid complex on carbon as a most general oxidation catalyst. This unique material allows for the synthesis of simple, functionalized, and structurally diverse (hetero)aromatic aldehydes, ketones, carboxylic acids, esters, nitriles, and amides from alcohols in excellent yields in the presence of air.
- Bartling, Stephan,Beller, Matthias,Chandrashekhar, Vishwas G.,Jagadeesh, Rajenahally V.,Rabeah, Jabor,Rockstroh, Nils,Senthamarai, Thirusangumurugan
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supporting information
p. 508 - 531
(2022/02/11)
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- 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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- 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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supporting information
p. 6982 - 6986
(2021/09/08)
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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 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 0046-0050
(2020/11/09)
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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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- 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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- 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 0094-0101
(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 0068-0075
(2019/12/02)
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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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- Copper-Catalyzed Electrophilic Thiolation of Organozinc Halides by Using N-Thiophthalimides Leading to Polyfunctional Thioethers
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(Hetero)aryl, benzylic, and alkyl zinc halides were thiolated with N-thiophthalimides at 25 °C within 1 h in the presence of 5–10 % Cu(OAc)2?H2O to furnish the corresponding polyfunctionalized thioethers in good yields. This electrop
- Gra?l, Simon,Hamze, Clémence,Koller, Thadd?us J.,Knochel, Paul
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p. 3752 - 3755
(2019/02/13)
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- Synthesis of vinyl and electron-deficient aryl trifluoromethyl sulfides via Csp2?OH bond activation with AgSCF3 and n-Bu4NI/KI
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Direct dehydroxytrifluoromethylthiolation of enols and electron-deficient phenols with AgSCF3 in the presence of n-Bu4NI and KI is reported, affording a series of vinyl and aryl trifluoromethyl sulfides in moderate to excellent yields. This work represents a rare example of direct functionalization of Csp2?OH bonds.
- Liu, Yin-Li,Xu, Xiu-Hua,Qing, Feng-Ling
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p. 5827 - 5832
(2018/09/21)
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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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- 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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- Synthesis of nitriles from amines using nanoscale Co3O4-based catalysts via sustainable aerobic oxidation
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The selective oxidation of amines for the benign synthesis of nitriles under mild conditions is described. Key to success for this transformation is the application of reusable cobalt oxide-based nanocatalysts. The resulting nitriles constitute key precursors and central intermediates in organic synthesis.
- Natte, Kishore,Jagadeesh, Rajenahally V.,Sharif, Muhammad,Neumann, Helfried,Beller, Matthias
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supporting information
p. 3356 - 3359
(2016/04/09)
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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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- 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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- 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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- 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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- 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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- "Nanorust"-catalyzed benign oxidation of amines for selective synthesis of nitriles
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Organic nitriles constitute key precursors and central intermediates in organic synthesis. In addition, nitriles represent a versatile motif found in numerous medicinally and biologically important compounds. Generally, these nitriles are synthesized by traditional cyanation procedures using toxic cyanides. Herein, we report the selective and environmentally benign oxidative conversion of primary amines for the synthesis of structurally diverse aromatic, aliphatic and heterocyclic nitriles using a reusable "nanorust" (nanoscale Fe2O3)-based catalysts applying molecular oxygen.
- Jagadeesh, Rajenahally V.,Junge, Henrik,Beller, Matthias
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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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- 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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- 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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