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Overriding the alkynophilicity of gold: catalytic pathways from higher energy Au(I)-substrate complexes and reactant deactivation via unproductive complexation in the gold(I)-catalyzed propargyl Claisen rearrangement.
- Source :
-
Organic & biomolecular chemistry [Org Biomol Chem] 2013 Feb 13; Vol. 11 (10), pp. 1624-30. - Publication Year :
- 2013
-
Abstract
- Computational and experimental analysis of unusual substituent effects in the Au-catalyzed propargyl Claisen rearrangement revealed new features important for the future development of Au(I) catalysis. Despite the higher stability of Au-alkyne complexes, they do not always correspond to the catalytically active compounds. Instead, the product emanates from the higher energy Au(I)-oxygen complex reacting via a low barrier cation-accelerated oxonia Claisen pathway. Additionally, both intra and intermolecular competition from other Lewis bases present in the system, for the Au(I) catalyst, can lead to unproductive stabilization of the substrate/catalyst complex, explaining hitherto unresolved substituent effects.
Details
- Language :
- English
- ISSN :
- 1477-0539
- Volume :
- 11
- Issue :
- 10
- Database :
- MEDLINE
- Journal :
- Organic & biomolecular chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 23307145
- Full Text :
- https://doi.org/10.1039/c2ob27231h