14038-06-3Relevant articles and documents
Preparation and Characterization of Pentafluoro-λ6-sulfanyldifluoromethane and Pentafluoro-λ6-sulfanyl-1,1,2,2-tetrafluoroethane
Belina, Steven P.,Qing, Si-Yan,Dudziński, Piotr,Matsnev, Andrej V.,Mück-Lichtenfeld, Christian,Haufe, Günter,Thrasher, Joseph S.
, (2021/09/14)
The pentafluorosulfanyl-λ6-perfluoroalkyl halides SF5CF2I, SF5CF2CF2Br, and SF5CF2CF2I were prepared for use in the syntheses of other SF5-contai
Unusual Electronic Effects of Ancillary Ligands on the Perfluoroalkylation of Aryl Iodides and Bromides Mediated by Copper(I) Pentafluoroethyl Complexes of Substituted Bipyridines
Kalkman, Eric D.,Mormino, Michael G.,Hartwig, John F.
supporting information, p. 19458 - 19465 (2019/12/25)
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.
"ligandless" Pentafluoroethylation of Unactivated (Hetero)aryl and Alkenyl Halides Enabled by the Controlled Self-Condensation of TMSCF3-Derived CuCF3
Mestre, Jordi,Castillón, Sergio,Boutureira, Omar
supporting information, p. 15087 - 15097 (2019/11/03)
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
A Convenient Method for Catalytic Aromatic Pentafluoroethylation Using Potassium (Pentafluoroethyl)trimethoxyborate
Sugiishi, Tsuyuka,Kawauchi, Daisuke,Sato, Mizuki,Sakai, Tatsuya,Amii, Hideki
, p. 1874 - 1878 (2017/04/06)
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.
A class of effective decarboxylative perfluoroalkylating reagents: [(phen)2Cu](O2CRF)
Huang, Yangjie,Ajitha, Manjaly J.,Huang, Kuo-Wei,Zhang, Zhongxing,Weng, Zhiqiang
supporting information, p. 8468 - 8474 (2016/06/01)
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.
PENTAFLUOROETHYLATING COMPOSITIONS
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Page/Page column 37; 38; 39, (2015/02/25)
The present invention relates to pentafluoroethylating compositions, processes for obtaining them, and their use in pentafluoroethylation reactions.
Stable but reactive perfluoroalkylzinc reagents: Application in ligand-free copper-catalyzed perfluoroalkylation of aryl iodides
Aikawa, Kohsuke,Nakamura, Yuzo,Yokota, Yuki,Toya, Wataru,Mikami, Koichi
supporting information, p. 96 - 100 (2015/02/05)
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.
Pentafluoroethylating compositions
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Paragraph 0194, (2015/02/25)
The present invention relates to pentafluoroethylating compositions, processes for obtaining them, and their use in pentafluoroethylation reactions.
Direct synthesis of pentafluoroethyl copper from pentafluoropropionate as an economical C2F5 source: Application to pentafluoroethylation of arylboronic acids and aryl bromides
Serizawa, Hiroki,Aikawa, Kohsuke,Mikami, Koichi
supporting information, p. 3456 - 3459 (2014/07/21)
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.
Cupration of C2F5H: Isolation, structure, and synthetic applications of [K(DMF)2][(t -BuO)Cu(C2F 5)]. Highly efficient pentafluoroethylation of unactivated aryl bromides
Lishchynskyi, Anton,Grushin, Vladimir V.
supporting information, p. 12584 - 12587 (2013/09/23)
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.
