- Preparation and Characterization of Pentafluoro-λ6-sulfanyldifluoromethane and Pentafluoro-λ6-sulfanyl-1,1,2,2-tetrafluoroethane
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The pentafluorosulfanyl-λ6-perfluoroalkyl halides SF5CF2I, SF5CF2CF2Br, and SF5CF2CF2I were prepared for use in the syntheses of other SF5-contai
- Belina, Steven P.,Qing, Si-Yan,Dudziński, Piotr,Matsnev, Andrej V.,Mück-Lichtenfeld, Christian,Haufe, Günter,Thrasher, Joseph S.
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- Unusual Electronic Effects of Ancillary Ligands on the Perfluoroalkylation of Aryl Iodides and Bromides Mediated by Copper(I) Pentafluoroethyl Complexes of Substituted Bipyridines
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Several perfluoroalkylcopper compounds have been reported previously that serve as reagents or catalysts for the perfluoroalkylation of aryl halides. However, the relationships between the reactivity of such complexes and the electronic properties of the ancillary ligands are unknown, and such relationships are not well-known in general for copper complexes that mediate or catalyze cross coupling. We report the synthesis and characterization of a series of pentafluoroethylcopper(I) complexes ligated by bipyridine ligands possessing varied electronic properties. In contrast to the limited existing data on the reactivity of L2Cu(I)-X complexes bearing amine and pyridine-type ligands in Ullmann-type aminations with aryl halides, the reactions of aryl halides with pentafluoroethylcopper(I) complexes bearing systematically varied bipyridine ligands were faster for complexes bearing less electron-donating bipyridines than for complexes bearing more electron-donating bipyridines. Analysis of the rates of reaction and the relative populations of the neutral complexes [(R2bpy)CuC2F5] and ionic complexes [(R2bpy)2Cu][Cu(C2F5)2] formed by these reagents in solution suggests that this effect of electronics on the reaction rate results from an unusual trend of faster oxidative addition of aryl halides to [(R2bpy)CuC2F5] complexes containing less electron-donating R2bpy ligands than to those containing more electron-donating R2bpy ligands.
- Kalkman, Eric D.,Mormino, Michael G.,Hartwig, John F.
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supporting information
p. 19458 - 19465
(2019/12/25)
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- "ligandless" Pentafluoroethylation of Unactivated (Hetero)aryl and Alkenyl Halides Enabled by the Controlled Self-Condensation of TMSCF3-Derived CuCF3
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Pentafluoroethylation of unactivated C(sp2)-X bonds (X = I, Br) using a storable, "ligandless" CuC2F5 reagent prepared by controlled self-condensation of ready available TMSCF3-derived CuCF3 has been
- Mestre, Jordi,Castillón, Sergio,Boutureira, Omar
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supporting information
p. 15087 - 15097
(2019/11/03)
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- A Convenient Method for Catalytic Aromatic Pentafluoroethylation Using Potassium (Pentafluoroethyl)trimethoxyborate
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A method for the copper-catalyzed pentafluoroethylation of aryl iodides using potassium (pentafluoroethyl)trimethoxyborate has been developed. The borate was found to be a convenient pentafluoroethyl source. In parallel, it was found that the solvent, as well as ligand, makes significant impact on the catalytic perfluoroalkylations.
- Sugiishi, Tsuyuka,Kawauchi, Daisuke,Sato, Mizuki,Sakai, Tatsuya,Amii, Hideki
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p. 1874 - 1878
(2017/04/06)
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- A class of effective decarboxylative perfluoroalkylating reagents: [(phen)2Cu](O2CRF)
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This article describes the invention of a class of effective reagents [(phen)2Cu](O2CRF) (1) for the decarboxylative perfluoroalkylation of aryl and heteroaryl halides. Treatment of copper tert-butyloxide with phenanthroline ligands, with subsequent addition of perfluorocarboxylic acids afforded air-stable copper(i) perfluorocarboxylato complexes 1. These complexes reacted with a variety of aryl and heteroaryl halides to form perfluoroalkyl(hetero)arenes in moderate to high yields. Computational studies suggested that the coordination of the second phen ligand may reduce the energy barrier for the decarboxylation of perfluorocarboxylate to facilitate perfluoroalkylation.
- Huang, Yangjie,Ajitha, Manjaly J.,Huang, Kuo-Wei,Zhang, Zhongxing,Weng, Zhiqiang
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supporting information
p. 8468 - 8474
(2016/06/01)
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- PENTAFLUOROETHYLATING COMPOSITIONS
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The present invention relates to pentafluoroethylating compositions, processes for obtaining them, and their use in pentafluoroethylation reactions.
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Page/Page column 37; 38; 39
(2015/02/25)
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- Stable but reactive perfluoroalkylzinc reagents: Application in ligand-free copper-catalyzed perfluoroalkylation of aryl iodides
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The aromatic perfluoroalkylation catalyzed by a copper(I) salt with bis(perfluoroalkyl)zinc reagents Zn(RF)2(DMPU)2, which were prepared and then isolated as a stable white powder from perfluoroalkyl iodide and diethylzinc, was accomplished to provide the perfluoroalkylated products in good-to-excellent yields. The advantages of this reliable and practical catalytic reaction are 1) airstable and easy-to-handle bis(perfluoroalkyl)zinc reagents can be utilized, 2) the reagent is reactive and hence the operation without activators and ligands is simple, and 3) not only trifluoromethylation but also perfluoroalkylation can be attained.
- Aikawa, Kohsuke,Nakamura, Yuzo,Yokota, Yuki,Toya, Wataru,Mikami, Koichi
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supporting information
p. 96 - 100
(2015/02/05)
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- Pentafluoroethylating compositions
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The present invention relates to pentafluoroethylating compositions, processes for obtaining them, and their use in pentafluoroethylation reactions.
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Paragraph 0194
(2015/02/25)
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- Direct synthesis of pentafluoroethyl copper from pentafluoropropionate as an economical C2F5 source: Application to pentafluoroethylation of arylboronic acids and aryl bromides
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The direct synthesis of pentafluoroethyl copper (CuC2F 5) from a cuprate reagent and ethyl pentafluoropropionate as one of the most economical and useful pentafluoroethyl sources was accomplished. The advantages of this method are; all the reagents employed are low-cost and operationally simple, and the CuC2F5 reagent is prepared in virtually quantitative yield. Furthermore, the CuC2F5 reagent prepared was successfully applied to two types of pentafluoroethylations with arylboronic acids and aryl bromides to provide the pentafluoroethylated aromatic products in good-to-excellent yields, including large scale operations.
- Serizawa, Hiroki,Aikawa, Kohsuke,Mikami, Koichi
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supporting information
p. 3456 - 3459
(2014/07/21)
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- Cupration of C2F5H: Isolation, structure, and synthetic applications of [K(DMF)2][(t -BuO)Cu(C2F 5)]. Highly efficient pentafluoroethylation of unactivated aryl bromides
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Pentafluoroethane, C2F5H (HFC-125), is smoothly cuprated with preisolated or in situ-generated [K(DMF)][(t-BuO)2Cu] to give [K(DMF)2][(t-BuO)Cu(C2F5)] (1) in nearly quantitative yield. Complex 1 has been isolated, structurally characterized, and demonstrated to be an exceedingly versatile pentafluoroethylating reagent for a variety of substrates, including unactivated aryl bromides.
- Lishchynskyi, Anton,Grushin, Vladimir V.
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supporting information
p. 12584 - 12587
(2013/09/23)
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- A general strategy for the perfluoroalkylation of arenes and arylbromides by using arylboronate esters and [(phen)CuRF]
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A versatile method for the synthesis of aryl perfluoroalkanes from arenes and aryl bromides is described. Substituted arenes or aryl bromides are converted in situ to an aryl boronate ester that readily undergoes perfluoroalkylation in air with [(phen)CuRF]. A broad range of aryl bromide substrates were perfluoroalkylated in good yield for the first time. [(phen)CuCF3] is now commercially available and has been prepared on 20g scale. Copyright
- Litvinas, Nichole D.,Fier, Patrick S.,Hartwig, John F.
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supporting information; experimental part
p. 536 - 539
(2012/02/16)
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- NOVEL BENZAMIDES, PRODUCTION THEREOF, AND USE THEREOF AS MEDICAMENTS
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Heteroaryloxy-substituted benzoic acid amides of general formula I wherein the groups R1 to R7 as well as X and Y are defined according to claim 1, including the tautomers, the stereoisomers, the mixtures and the salts thereof. The compounds according to the invention are suitable for the treatment of respiratory complaints, particularly COPD and asthma.
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Page/Page column 78
(2012/05/07)
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- 7-(Piperazine-1-Ymethyl)-1H-Indole-2-Carboxylic Acid (Phenyl)-Amide Derivatives and Allied Compounds as P38 Map Kinase Inhibitors for the Treatment of Respiratory Diseases
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The present invention provides compounds according to general formula (I) which are proposed for the treatment of respiratory complaints, particularly asthma and COPD.
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Page/Page column 60
(2011/11/12)
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- 2-Amido-4-phenylthiazole Derivatives, The Preparation And The Therapeutic Use Thereof
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The disclosure relates to 2-amido-4-phenylthiazole derivatives of general formula (I) below: in which R1, R2, R3, Y, m, n, and p are as defined in the disclosure; as well as to their isomers, salts and solvates, to the pharmaceutical compositions containing them and to the therapeutic use thereof.
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Page/Page column 10
(2008/06/13)
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- 2-carbamide-4-phenylthiazole derivatives, preparation thereof and therapeutic use thereof
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The disclosure concerns 2-carbamide-4-phenylthiazole derivatives of general formula (I). The disclosure also concerns pharmaceutical compositions containing a compound of general formula (I) and to processes for preparing and methods of using compounds of
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Page/Page column 12
(2010/11/28)
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- Nucleophilic trifluoromethylation of aryl halides with methyl trifluoroacetate
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When associated with an alkaline halide, such as cesium fluoride or cesium chloride, and Cu(I) species, methyl trifluoroacetate (MTFA) constitutes a valuable trifluoromethylating agent for substituting aromatic (or heteroaromatic) iodides and bromides. The reaction can be carried out in DMF at 180 °C or, better, in sulfolane which allows he reaction to proceed at a lower temperature (from 140 °C).
- Langlois, Bernard R.,Roques, Nicolas
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p. 1318 - 1325
(2008/02/10)
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- 2-Acylamino-4-phenylthiazole derivatives, preparation thereof and therapeutic application thereof
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The invention relates to 2-acylamino-4-phenylthiazole derivatives of general formula (I): pharmaceutically acceptable acid-addition salts thereof, hydrates or solvates of such derivatives or such pharmaceutically acceptable acid addition salts, intermediates thereto, processes for the preparation thereof, and therapeutic application thereof.
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Page/Page column 18
(2008/06/13)
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- FLUORINATED PHENYL-NAPHTHALENYL-UREA COMPOUNDS AS INHIBITORS OF CYTOKINES INVOLVED IN INFLAMMATORY PROCESSES
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Disclosed are compounds of formula (I) wherein R1, R2, W and X of formula (I) are defined herein. The compounds inhibit production of cytokines involved in inflammatory processes and are thus useful for treating diseases and pathological conditions involving inflammation such as chronic inflammatory disease. Also disclosed are processes for preparing these compounds and pharmaceutical compositions comprising these compounds.
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- A NOVEL AND CONVENIENT METHOD FOR TRIFLUOROMETHYLATION OF ORGANIC HALIDES USING CF3SiR'3/KF/Cu(I) SYSTEM
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Fluoride ion induced cross-coupling reaction of organic halides with trifluoromethyltrialkylsilanes takes place in the presence of Cu(I) salts under mild reaction conditions to give the corresponding trifluoromethylated products in high yields.
- Urata, Hisao,Fuchikami, Takamasa
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- A CONVENIENT SYNTHESIS OF PENTAFLUOROETHYL-SUBSTITUTED AROMATICS
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The reaction of substituted aryl bromides and iodides with potassium pentafluoropropionate and copper (I) iodide in DMF/toluene at 150 deg C gives good yields of the corresponding aryl pentafluoroethyl compounds.
- Freskos, John N.
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p. 965 - 972
(2007/10/02)
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- PERFLUOROALKYLATION OF AROMATIC COMPOUNDS WITH RfI(Ph)OSO2CF3
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Perfluoroalkylation of various aromatic compounds with perfluoroalkylphenyliodonium trifluoromethanesulfonate (FITS) under mild conditions was described.The reactivity of other perfluoroalkyliodonium salts was also examined.
- Umemoto, Teruo,Kuriu, Yuriko,Shuyama, Hideo
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p. 1663 - 1666
(2007/10/02)
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- Studies on Organic Fluorine Compounds. Part 27. Abnormal Reactions in the Trifluoromethylation of Aromatic Compounds with Trifluoromethyl Iodide and Copper Powder
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Reaction of 3-bromobenzofuran with trifluoromethyl iodide and copper powder in pyridine gave 2-(trifluoromethyl)-, 2- and 3-(pentafluoroethyl)-, and 2,3-bis(trifluoromethyl)-benzofuran, as well as the expected product, 3-(trifluoromethyl)benzofuran.Bromoanisole also gave (trifluoromethyl)anisole and (pentafluoroethyl)anisole, but introduction of the perfluoroalkyl group occurred at the position originally occupied by the bromine.Formation of pentafluoroethyl compounds is explained by decomposition of trifluoromethylcopper to cuprous fluoride and difluorocarbene, which can then react with a further molecule of trifluoromethylcopper to form pentafluoroethylcopper.This then reacts with aryl halide to give pentafluoroethyl compounds.Perfluoroalkylcopper is thermally cleaved to perfluoroalkyl radical, which then reacts with pyridine to give perfluoroalkylpyridines.This mechanism must be involved in the formation of 2,3-bis(trifluoromethyl)benzofuran.Introduction of a perfluoroalkyl group to the position originally unoccupied with halogen might be due to the rather localized double bond in benzofuran.
- Kobayashi, Yoshiro,Kumadaki, Itsumaro
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p. 661 - 664
(2007/10/02)
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