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Turning unreactive copper acetylides into remarkably powerful and mild alkyne transfer reagents by oxidative umpolung.

Authors
  • Evano, G
  • Jouvin, K
  • Theunissen, C
  • Guissart, C
  • Laouiti, A
  • Tresse, C
  • Heimburger, J
  • Bouhoute, Y
  • Veillard, R
  • Lecomte, M
  • Nitelet, A
  • Schweizer, S
  • Blanchard, N
  • Alayrac, C
  • Gaumont, A-C
Type
Published Article
Journal
Chemical Communications
Publisher
The Royal Society of Chemistry
Publication Date
Sep 11, 2014
Volume
50
Issue
70
Pages
10008–10018
Identifiers
DOI: 10.1039/c4cc03198a
PMID: 24911768
Source
Medline
License
Unknown

Abstract

This is not breaking news: copper acetylides, readily available polymeric rock-stable solids, have been known for more than a century to be unreactive species and piteous nucleophiles. This lack of reactivity actually makes them ideal alkyne transfer reagents that can be easily activated under mild oxidizing conditions. When treated with molecular oxygen in the presence of simple chelating nitrogen ligands such as TMEDA, phenanthroline or imidazole derivatives, they are smoothly oxidized to highly electrophilic species that formally behave like acetylenic carbocations and can therefore be used for the mild and practical alkynylation of a wide range of nitrogen, phosphorus and carbon nucleophiles.

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