Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 20, Issue 3, Pages 683-688Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201304087
Keywords
acetylides; alkynes; dual activation; gold intermediates; ligand effects
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Funding
- Spanish Ministerio de Ciencia e Innovacion
- European Community Founds (FEDER)
- Generalitat Valenciana [CTQ 2010-19999, CSD2007-00006, ACOMP-2013/185]
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The competition between - and dual sigma,-gold-activation modes is revealed in the gold(I)-catalyzed heterocyclization of 1-(o-ethynylaryl)urea. A noticeable effect of various ligands in gold complexes on the choice of these activation modes is described. The cationic [Au(IPr)](+) (IPr=2,6-bis(diisopropylphenyl)imidazol-2-ylidene) complex cleanly promotes the activation of terminal alkynes, whereas [Au(PtBu3)](+) favors intermediate sigma, species. In this experimental and mechanistic study, which includes kinetic and cross-over experiments, several sigma-gold, sigma,-gold, and other gold polynuclear reaction intermediates have been isolated and identified by NMR spectroscopy, X-ray diffraction, or MALDI spectrometry. The ligand control in the simultaneous or alternative - and sigma,-activation modes is also supported by deuterium-labeling experiments.
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