1092349-84-2

Upstream product

• 61358-25-6 bis(4-tert-butylphenyl)iodonium hexafluorophosphate 
• 75-05-8 acetonitrile 
• 116-14-3 polytetrafluoroethylene 
• 35779-04-5 1-tert-butyl-4-iodobenzene 
• 3972-65-4 1-bromo-4-tert-butylbenzene 
• 124898-13-1 trimethyl(pentafluoroethyl)silane 
• 60007-39-8 pentafluoroethylcopper(I) 
• 123324-71-0 p-tert-butylphenylboronic acid 

Relevant academic research and scientific papers

Solvated Nickel Complexes as Stoichiometric and Catalytic Perfluoroalkylation Agents**

The acetonitrile-solvated [(MeCN)Ni(C2F5)3]? was prepared in order to compare and contrast its reactivity with the known [(MeCN)Ni(CF3)3]? towards organic electrophiles. Both [(MeCN)Ni(CF3)3]? and [(MeCN)Ni(C2F5)3]? successfully react with aryl iodonium and diazonium salts as well as alkynyl iodonium salts to give fluoroalkylated organic products. Electrochemical analysis of [(MeCN)NiII(C2F5)3]? suggests that, upon electro-oxidation to [(MeCN)nNiIII(C2F5)3], reductive homolysis of a perfluoroethyl radical occurs, with the concomitant formation of [(MeCN)2NiII(C2F5)2]. Catalytic C?H trifluoromethylations of electron-rich arenes were successfully achieved using either [(MeCN)Ni(CF3)3]? or the related [Ni(CF3)4]2?. Stoichiometric reactions of the solvated nickel complexes reveal that “ligandless” nickel is exceptionally capable of serving as reservoir of CF3 groups under catalytically relevant conditions.

CuI-Catalyzed Pentafluoroethylation of Aryl Iodides in the Presence of Tetrafluoroethylene and Cesium Fluoride: Determining the Route to the Key Pentafluoroethyl CuI Intermediate

The Cu(I)-catalyzed pentafluoroethylation of iodoarenes via the fluorocupration of tetrafluoroethylene (TFE) is disclosed. The active species, (phen)CuC2F5, was isolated and its molecular structure confirmed by a single-crystal X-ray diffraction analysis. The key to the successful suppression of the competing oligomerization of TFE is to refrain from stirring the reaction mixture. A mechanistic study clearly discarded the possibility that the catalytic reaction proceeds via a radical pathway.

From C1 to C2: TMSCF3 as a Precursor for Pentafluoroethylation

A highly efficient copper-mediated aromatic pentafluoroethylation method using TMSCF3 as the sole fluoroalkyl source is described. The reaction proceeds by a key C1 to C2 process, that is, the generation of CuCF3 from TMSCF3, followed by a subsequent spontaneous transformation into CuC2F5. Various aryl iodides were pentafluoroethylated with the TMSCF3-derived CuC2F5. This method represents the first practical and efficient method for pentafluoroethylation of aryl iodides using commercially available TMSCF3 as a pentafluoroethyl precursor.

Stoichiometric and Catalytic Aryl-Perfluoroalkyl Coupling at Tri-tert-butylphosphine Palladium(II) Complexes

This Communication describes studies of Ph-RF (RF = CF3 or CF2CF3) coupling at Pd complexes of general structure (PtBu3)PdII(Ph)(RF). The CF3 analogue participates in fast Ph-CF3 coupling (II complex. Furthermore, they show that this undesired pathway can be circumvented by changing from a CF3 to a CF2CF3 ligand. Ultimately, the insights gained from stoichiometric studies enabled the identification of Pd(PtBu3)2 as a catalyst for the Pd-catalyzed cross-coupling of aryl bromides with TMSCF2CF3 to afford pentafluoroethylated arenes.

A class of effective decarboxylative perfluoroalkylating reagents: [(phen)2Cu](O2CRF)

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

The present invention relates to pentafluoroethylating compositions, processes for obtaining them, and their use in pentafluoroethylation reactions.

Pentafluoroethylating compositions

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

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.

Direct synthesis of pentafluoroethyl copper from pentafluoropropionate as an economical C2F5 source: Application to pentafluoroethylation of arylboronic acids and aryl bromides

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

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.