Issue 45, 2015

Approaches to prepare perfluoroalkyl and pentafluorophenyl copper couples for cross-coupling reactions with organohalogen compounds

Abstract

The reactions of iodoperfluoroalkanes CnF2n+1I (n = 2, 3, 4) and n-BuLi at low temperatures give NMR spectroscopic evidence for LiCnF2n+1 which were converted into LiCu(CnF2n+1)2 derivatives upon treatment with 0.5 mol copper(I) bromide, CuBr. An alternative route to obtain perfluoroorgano copper couples, Cu(Rf)2Ag (Rf = n-C3F7, n-C4F9, C6F5) was achieved from the reactions of the corresponding perfluoroorgano silver(I) reagents, AgRf, and elemental copper through redox transmetallations. The composition of the resulting reactive intermediates was investigated by means of 19F NMR spectroscopy and ESI mass spectrometry. Perfluoro-n-propyl and perfluoro-n-butyl copper–silver reagents prepared by the oxidative transmetallation route exhibited good properties in C–C bond formation reactions with acid chlorides even under moderate conditions. Substitution of bromine directly bound to aromatics for perfluoroalkyl groups was achieved at elevated temperatures, while success in halide substitution reactions using lithium copper couples remained poor.

Graphical abstract: Approaches to prepare perfluoroalkyl and pentafluorophenyl copper couples for cross-coupling reactions with organohalogen compounds

  • This article is part of the themed collection: Fluorine

Article information

Article type
Paper
Submitted
29 Jul 2015
Accepted
13 Oct 2015
First published
13 Oct 2015

Dalton Trans., 2015,44, 19693-19699

Author version available

Approaches to prepare perfluoroalkyl and pentafluorophenyl copper couples for cross-coupling reactions with organohalogen compounds

M. M. Kremlev, A. I. Mushta, W. Tyrra, Y. L. Yagupolskii, D. Naumann and M. Schäfer, Dalton Trans., 2015, 44, 19693 DOI: 10.1039/C5DT02925B

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