1092349-84-2Relevant articles and documents
Solvated Nickel Complexes as Stoichiometric and Catalytic Perfluoroalkylation Agents**
Shreiber, Scott T.,Vicic, David A.
supporting information, p. 18162 - 18167 (2021/07/14)
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.
From C1 to C2: TMSCF3 as a Precursor for Pentafluoroethylation
Xie, Qiqiang,Li, Lingchun,Zhu, Ziyue,Zhang, Rongyi,Ni, Chuanfa,Hu, Jinbo
supporting information, p. 13211 - 13215 (2018/09/25)
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.
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.
