- New stable reagents for the nucleophilic trifluoromethylation. Part 4: Trifluoromethylation of disulfides and diselenides with hemiaminals of trifluoroacetaldehyde
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Hemiaminals of fluoral and derivatives have been previously described as efficient new reagents for the nucleophilic trifluoromethylation of carbonyl compounds. Their use has been extended to the synthesis of trifluoromethyl sulfides and selenides from di
- Blond, G.,Billard, T.,Langlois
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Read Online
- A New and Efficient Method for the Synthesis of Trifluoromethylthio- and Selenoethers
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(Equation presented) A new atom-economic procedure for preparation of trifluoromethyl thio- and selenoethers is reported, wherein both halves of aryl and alkyl disulfides and diselenides are able to be utilized with high efficiency.
- Pooput, Chaya,Medebielle, Maurice,Dolbier Jr., William R.
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Read Online
- Nucleophilic perfluoroalkylation of diaryldisulfides with perfluorocarboxylate salts
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A new industrial and economical route to trifluoromethyl aryl sufides by thermal decarboxylation of trifluoroacetate salts has been recently developed. The possibility of generalising this reaction of "trifluorodecarboxylation" to RfCO2K (Rf: CCl3, CF2Cl, CF3CF2, CF3CF2CF2) in order to synthesise RfSAr has been studied. Thus, the reaction was effective with RfCO2K (Rf=CCl3, CF3CF2) and a new route to aryl pentafluoroethyl sufides CF3CF2SAr has been briefly exemplified.
- Roques, Nicolas
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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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- 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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- Trifluoromethyl Thianthrenium Triflate: A Readily Available Trifluoromethylating Reagent with Formal CF3+, CF3?, and CF3-Reactivity
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Here we report the synthesis and application of trifluoromethyl thianthrenium triflate (TT-CF3+OTf-) as a novel trifluoromethylating reagent, which is conveniently accessible in a single step from thianthrene and triflic anhydride. We demonstrate the use of TT-CF3+OTf- in electrophilic, radical, and nucleophilic trifluoromethylation reactions.
- Jia, Hao,H?ring, Andreas P.,Berger, Florian,Zhang, Li,Ritter, Tobias
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supporting information
p. 7623 - 7628
(2021/05/26)
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- The First Organosilver(III) Fluoride, [PPh4][(CF3)3AgF]
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Organosilver(III) fluoride complexes have been assigned a key role in different fluorination processes. To the best of our knowledge, however, none of them seem to have been isolated or even detected thus far. Here we report on the successful synthesis of the trifluoromethyl derivative [PPh4][(CF3)3AgF], which has been isolated in high yield. The thermodynamic stability of the Ag?F bond is shown by calculation and demonstrated by multistage mass spectrometry (MSn) under collision-induced dissociation (CID) conditions. Nevertheless, the substantial elongation found in the Ag?F bond (X-ray) is correlated with a marked nucleophilic character of the terminal F ligand. This Ag?F bond is, in fact, quite reactive: it suffers hydrolysis and is also solvolyzed by thiols.
- Joven-Sancho, Daniel,Baya, Miguel,Martín, Antonio,Orduna, Jesús,Menjón, Babil
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supporting information
p. 4471 - 4475
(2020/02/27)
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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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- Ortho-lithiation reaction of aryl triflones
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The ortho-lithiation of substituted arenes is a powerful methodology to synthesize ortho-substituted arenes. While a wide variety of directed metalation groups (DMGs) have been reported, trifluoromethyl sulfone has never been used. We disclose the first example of ortho-lithiation of aryl triflones. We found that the trifluoromethyl sulfonyl group is not only an important structural motif in biologically active molecules and specialty materials, but also an excellent DMG moiety for ortho-metalation reactions. The use of a base that causes steric hindrance, LTMP, is the key for successful transformation to furnish a variety of ortho-substituted aryl triflones in good yields. Further functionalization of resulting ortho-substituted aryl triflones was demonstrated by metal-catalyzed coupling reactions.
- Sumii, Yuji,Taniguchi, Misaki,Xu, Xiu-Hua,Tokunaga, Etsuko,Shibata, Norio
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p. 5635 - 5641
(2018/08/17)
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- Synthesis of Chloro(phenyl)trifluoromethyliodane and Catalyst-Free Electrophilic Trifluoromethylations
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The present work deals with a challenge in the synthesis of aryltrifluoromethyliodanes (ArICF3X) and develops a direct route to PhICF3Cl via a simple ligand-exchange reaction of PhI(OCOCF3)2, Me3SiCF3, and NaCl for the first time. The I-Cl bond length in PhICF3Cl supports its iodonium character, which enables an enhanced CF3-transfer capability in electrophilic S-, O-, N-, and C-trifluoromethylations as well as in catalyst-free trifluoromethylation-cyclizations of arylisonitriles.
- Xu, Cong,Song, Xiaoning,Guo, Jia,Chen, Sibao,Gao, Jie,Jiang, Jing,Gao, Fengyun,Li, Yuxin,Wang, Mang
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supporting information
p. 3933 - 3937
(2018/07/22)
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- Borazine-CF3? Adducts for Rapid, Room Temperature, and Broad Scope Trifluoromethylation
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A fluoroform-derived borazine CF3? transfer reagent is used to effect rapid nucleophilic reactions in the absence of additives, within minutes at 25 °C. Inorganic electrophiles spanning seven groups of the periodic table can be trifluoromethylated in high yield, including transition metals used for catalytic trifluoromethylation. Organic electrophiles included (hetero)arenes, enabling C?H and C?X trifluoromethylation reactions. Mechanistic analysis supports a dissociative mechanism for CF3? transfer, and cation modification afforded a reagent with enhanced stability.
- Geri, Jacob B.,Wade Wolfe, Michael M.,Szymczak, Nathaniel K.
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supporting information
p. 1381 - 1385
(2018/01/15)
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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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- 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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- COMPLEXES FOR NUCLEOPHILIC, RADICAL, AND ELECTROPHILIC POLYFLUOROALKYLATION
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Disclosed herein are borazine complexes and use of the same in perfluoroalkylation reactions.
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Paragraph 00135
(2018/04/11)
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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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- 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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- 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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- 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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- 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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- 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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- 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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- First and second generation of trifluoromethanesulfenamide reagent: A trifluoromethylthiolating comparison
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Trifluoromethylthiolation of molecules is a more and more studied reaction. In particular, the direct electrophilic trifluoromethylthiolation plays an important role in this chemistry. Among the various developed reagents, trifluoromethanesulfenamides constitute an efficient family of reagents. However, no systematic comparison of these two generations has been realized. In this paper, the difference of reactivity of these reagents is studied towards various nucleophiles.
- Glenadel, Quentin,Alazet, Sébastien,Billard, Thierry
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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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- 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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- 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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- Electrophilic difluoro(phenylthio)methylation: Generation, stability, and reactivity of α-fluorocarbocations
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Electrophilic difluoro(phenylthio)methylation of allylsilanes has been achieved using bromodifluoro(phenylthio)methane (PhSCF2Br) and silver hexafluoroantimonate (AgSbF6). The structural assignment and observation of α-fluorocarbocation were substantiated by NMR and theoretical calculations. Detailed mechanistic and electronic studies have provided a fundamental understanding of the reactivity and stability of the difluoro(phenylthio)methylium cation (PhSCF2+).
- Betterley, Nolan M.,Surawatanawong, Panida,Prabpai, Samran,Kongsaeree, Palangpon,Kuhakarn, Chutima,Pohmakotr, Manat,Reutrakul, Vichai
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p. 5666 - 5669
(2013/12/04)
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- Amidinate salt of hexafluoroacetone hydrate for the preparation of fluorinated compounds by the release of trifluoroacetate
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A powerful, new reagent, an amidinate salt of hexafluoroacetone hydrate, is an air-stable salt that can be used for the preparation of fluorinated organic molecules. Nucleophilic trifluoromethylation reactions are demonstrated following the base-promoted release of trifluoroacetate. This reagent is soluble in many polar organic solvents and produces fluoroform, following the release of trifluoroacetate. Reactions with this reagent and common electrophiles provide excellent yields of trifluoromethylated products.
- Riofski, Mark V.,Hart, Allison D.,Colby, David A.
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supporting information
p. 208 - 211
(2013/04/10)
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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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- 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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- 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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- 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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- Sintered silicon carbide: A new ceramic vessel material for microwave chemistry in single-mode reactors
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Silicon carbide (SiC) is a strongly microwave absorbing chemically inert ceramic material that can be utilized at extremely high temperatures due to its high melting point and very low thermal expansion coefficient. Microwave irradiation induces a flow of electrons in the semiconducting ceramic that heats the material very efficiently through resistance heating mechanisms. The use of SiC carbide reaction vessels in combination with a single-mode microwave reactor provides an almost complete shielding of the contents inside from the electromagnetic field. Therefore, such experiments do not involve electromagnetic field effects on the chemistry, since the semiconducting ceramic vial effectively prevents microwave irradiation from penetrating the reaction mixture. The involvement of electromagnetic field effects (specific/nonthermal microwave effects) on 21 selected chemical transformations was evaluated by comparing the results obtained in microwave-transparent Pyrex vials with experiments performed in SiC vials at the same reaction temperature. For most of the 21 reactions, the outcome in terms of conversion/purity/product yields using the two different vial types was virtually identical, indicating that the electromagnetic field had no direct influence on the reaction pathway. Due to the high chemical resistance of SiC, reactions involving corrosive reagents can be performed without degradation of the vessel material. Examples include high-temperature fluorine-chlorine exchange reactions using triethylamine trihydrofluoride, and the hydrolysis of nitriles with aqueous potassium hydroxide. The unique combination of high microwave absorptivity, thermal conductivity, and effusivity on the one hand, and excellent temperature, pressure and corrosion resistance on the other hand, makes this material ideal for the fabrication of reaction vessels for use in microwave reactors. Simulating conductive heat transfer in a microwave: Using reaction vials made out of strongly microwave-absorbing silicon carbide (SiC) in a microwave reactor simulates a conductively heated autoclave experiment due to efficient shielding of the electromagnetic field by the SiC vial. Advantages of SiC vials for microwave processing include their excellent corrosion resistance, thermal stability, and high thermal effusivity and conductivity.
- Gutmann, Bernhard,Obermayer, David,Reichart, Benedikt,Prekodravac, Bojana,Irfan, Muhammad,Kremsner, Jennifer M.,Kappe, C. Oliver
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supporting information; experimental part
p. 12182 - 12194
(2011/02/23)
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- Alkoxide-induced nucleophilic trifluoromethylation using diethyl trifluoromethylphosphonate
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A novel alkoxide-induced nucleophilic trifluoromethylation of carbonyl compounds, disulfides, and diselenides using diethyl trifluoromethylphosphonate is presented. In these reactions diethyl trifluoromethylphosphonate acts as a [CF3-] synthon.
- Cherkupally, Prabhakar,Beier, Petr
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experimental part
p. 252 - 255
(2010/03/24)
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- Microwave-assisted aliphatic fluorine-chlorine exchange using triethylamine trihydrofluoride (TREAT-HF)
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Aliphatic fluorine-chlorine exchange reactions can be performed under microwave conditions using TREAT-HF as a mild and selective fluorination reagent. The highly polar TREAT-HF couples efficiently with microwave irradiation and reaction temperatures of 250 °C can be reached within 30 s. Under these conditions dichloromethyl- and trichloromethyl substrates can be converted into the corresponding fluoro analogs within 5 min. In order to prevent corrosion of borosilicate reaction vessel at high temperatures the use of sintered silicon carbide microwave vials is introduced.
- Kremsner, Jennifer M.,Rack, Michael,Pilger, Christian,Oliver Kappe
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supporting information; experimental part
p. 3665 - 3668
(2009/10/04)
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- Versatile application of trifluoromethyl triflate
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Hydrolytically stable and easy to handle trifluoromethyl triflate was found to be a liquid reservoir of 'masked' difluorophosgene. Anhydrous F- sources cleave the S-O bond in trifluoromethyl triflate yielding quantitatively the trifluoromethanolate salts, being useful trifluoromethoxy group carriers. Reaction of trifluoromethanolates with in situ generated from o-trimethylsilylphenyl triflate benzyne leads to (trifluoromethoxy)benzene and fluorobenzene (ratio 85:15). Whereas an addition of trifluoromethanethiolate anion across a triple bond of benzyne leads to [(trifluoromethyl)sulfanyl]benzene solely.
- Kolomeitsev, Alexander A.,Vorobyev, Mikhail,Gillandt, Hartmut
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p. 449 - 454
(2008/09/18)
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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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- Chlorodifluoromethyl phenyl sulfone: A novel non-ozone-depleting substance-based difluorocarbene reagent for O- and N-difluoromethylations
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Chlorodifluoromethyl phenyl sulfone, a previously unknown compound that can be readily prepared from non-ODS-based precursors, was found to act as a robust difluorocarbene reagent for O- and N-difluoromethylations. The Royal Society of Chemistry.
- Zheng, Ji,Li, Ya,Zhang, Laijun,Hu, Jinbo,Meuzelaar, Gerrit Joost,Federsel, Hans-Juergen
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p. 5149 - 5151
(2008/09/18)
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- An efficient preparation of new sulfonyl fluorides and lithium sulfonates
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(Formula Presented) An efficient preparation of several polyfluoroalkanesulfonyl fluorides is reported. This method, based on the synthesis of polyfluoroalkyl trimethyl silanes (precursors of polyfluoroalkylsulfinates) as intermediates, allows the successive transformations to be carried out in one pot. Moreover, these sulfonyl fluorides can be obtained from the corresponding sulfinates by electrophilic fluorination. This original approach avoids isolation and purification of some thermally or hydrolytically unstable intermediates. A series of new sulfonyl fluorides have been thus prepared from halogenodifluoromethylated precursors RCF2X (X = F, Br; R = ArC(O), ArS(O)n(CF2) m; n = 0, 1, 2; m = 1, 2) and have been transformed into the corresponding lithium sulfonates, which have potential applications as electrolytes for lithium batteries.
- Toulgoat, Fabien,Langlois, Bernard R.,Medebielle, Maurice,Sanchez, Jean-Yves
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p. 9046 - 9052
(2008/03/27)
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- Nucleophilic perfluoroalkylation of aldehydes, ketones, imines, disulfides, and diselenides
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Using a procedure analogous to that developed for nucleophilic trifluoromethylation, the perfluoroalkyl anion reagents created by mixing C 2F5I and n-C4F9I with tetrakis(dimethylamino)ethylene (TDAE) were effective in their nucleophilic reactions with aldehydes, ketones, imines, disulfides, and diselenides. Irradiation proved beneficial in the aldehyde and ketone reactions.
- Pooput, Chaya,Dolbier Jr., William R.,Medebielle, Maurice
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p. 3564 - 3568
(2007/10/03)
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- METHODS FOR NUCLEOPHILIC FLUOROMETHYLATION
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A novel, convenient and efficient method for trifluoromethylation of substrate compounds is disclosed. Particularly, alkoxide and hydroxide induced nucleophilic trifluoromethylation of carbonyl compounds, disulfides and other electrophiles, using phenyl trifluoromethyl sulfone PhSO2CF3 (or sulfoxide PhSOCF3) is disclosed. A method of both symmetrical and unsymmetrical anti-2,2-difluoropropan-1,3-diols with high diastereoselectivity (up to 94 % de) is disclosed using dufluoromethyl phenyl sulfone. This unusual type of high diastereoselectivity was obtained via an intramolecular charge-charge repulsion effect rather than the traditional steric control (based on the Cram's rule). Thus, difluoromethyl phenyl sulfone can be used as a novel difluoromethylene dianion species (`CF2""), which can couple two electrophiles (such as diphenyl disulfide or non-enolizable aldehydes) to give new difluoromethylenated products.
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- Synthesis of trifluoromethanesulfonic acid from CHF3
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Trifluoromethane is transformed to trifluoromethanesulfonic acid (TFMSA) at low temperature in a liquid-phase reaction in a strong acid such as fuming sulfuric acid as well as in a strong basic solution such as t-BuOK/DMF.
- Mukhopadhyay, Sudip,Bell, Alexis T.,Vijay Srinivas,Smith, Gary S.
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p. 660 - 662
(2013/09/02)
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- Alkoxide- and hydroxide-induced nucleophilic trifluoromethylation using trifluoromethyl sulfone or sulfoxide
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(Matrix presented) The first alkoxide- and hydroxide-induced nucleophilic trifluoromethylation of carbonyl compounds, disulfides, and other electrophiles, using phenyl trifluoromethyl sulfone 1a (sulfoxide 1b) is reported. The trifluoromethyl sulfone 1a or sulfoxide 1b acts as a CF3 - synthon. Both sulfone 1a and sulfoxide 1b are commercially available and can also be conveniently prepared from trifluoromethane. The new methodology provides a convenient route for efficient trifluoromethylation.
- Prakash, G. K. Surya,Hu, Jinbo,Olah, George A.
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p. 3253 - 3256
(2007/10/03)
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- Trifluoromethanesulfinic acid derivatives as nucleophilic trifluoromethylating reagents
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Secondary trifluoromethanesulfinamides and alkyl trifluoromethanesulfinates can be used as nucleophilic trifluoromethylating reagents towards various electrophiles by action of potassium tert-butoxide.
- Inschauspe, David,Sortais, Jean-Baptiste,Billard, Thierry,Langlois, Bernard R.
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p. 233 - 235
(2007/10/03)
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- Process of use in perfluoroalkyation and reactant for making use of this process
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The subject-matter of the present invention is a process of use in perfluoroalkylation and a reactant for making use of this process. This process is defined in that it comprises a stage in which a material of formula RfH and a base (or a species capable of generating a base) are brought into contact, in a polar and anhydrous medium, with a substrate carrying at least one electrophilic functional group. Application to organic synthesis.
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- Trifluoromethylating reagents and synthesizing processes
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A family of electrophilic trifluoromethylating reagents which can be synthesized by comparatively simple, inexpensive routes, and for which the reactivity can be varied according to need. A composition of matter according to the first embodiment of the invention comprises a compound having the formula: in which A comprises H or F and B comprises F, SCF3, OCF3, OCHF2, S+(CF3)C6H5, NO2or an NO2substituent. In a second embodiment of the invention, a process for preparing a trifluoromethyl diphenylsulfonium triflate compound corresponding to the formula shown above comprises reacting phenyl trifluoromethyl sulfoxide or one of its derivatives with an aromatic compound in which A comprises H or F and B comprises H, F, SCF3, OCF3, OCHF2, S+(CF3)C6H5, NO2or an NO2substituent. In a third embodiment of the invention, a trifluoromethylation process comprises reacting a trifluoromethyl diphenylsulfonium triflate corresponding to the formula shown above with an electron rich substrate.
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- Trifluoromethylthiodediazoniation: A simple, efficient route to trifluoromethyl aryl sulfides
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Copper(I) trifluoromethanethiolate reacts with a range of diazonium salts containing electron-withdrawing groups to give the corresponding trifluoromethyl aryl sulfides in high yield; it is also possible to carry out the diazotisation and trifluoromethylthiolation in one pot directly from the anilines.
- Adams, Dave J.,Goddard, Andrew,Clark, James H.,Macquarrie, Duncan J.
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p. 987 - 988
(2007/10/03)
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- Synthetic uses of thioesters of trifluoromethylated acids. Part 2: Reactions with alkenes
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The photolysis of trifluoromethanethiosulfonates (CF3SO2SR) or trifluorothioacetates (CF3COSR) in the presence of alkenes provides (trifluoromethyl)alkanes or β-sulfanyl (trifluoromethyl)alkanes. The formation of these compounds can be controlled by the nature and the ratio of the reactants. (C) 2000 Published by Elsevier Science Ltd.
- Billard, Thierry,Roques, Nicolas,Langlois, Bernard R.
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p. 3069 - 3072
(2007/10/03)
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- Bi(CF3)3/Cu(OCOCH3)2 - A new system for the synthesis of 2-trifluoromethylcycloalkan-1-ones, trifluoromethylanilines and phenyl(trifluoromethyl)sulfane
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Bi(CF3)3 reacts in the presence of equimolar amounts of Cu(OCOCH3)2 and 1-morpholinocyclopentene to give 1-morpholino-2-trifluoromethylcyclopentene in 83% yield. This compound as well as intermediately formed 1-morpholino-2-trifluoromethylcyclohexene can easily be converted into the corresponding cycloketones (78 and 41% yield) using the Swarts procedure. In absence of a copper(II) source, no reactions were observed. The reaction of the system Bi(CF3)3/Cu(OCOCH3)2 with N,N-diethylaniline gave an 1.7: 1 isomer mixture of 2-trifluoromethyl and 4-trifluormethyl-N,N-diethylanilines in 48% yield. With tetrabutylammonium thiophenolate, mixtures of phenyl(trifluoromethyl)sulfane and diphenyldisulfane were obtained. Mechanisms are discussed.
- Kirij,Pasenok,Yagupolskii,Tyrra,Naumann
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p. 217 - 221
(2007/10/03)
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