1,2-N-Migration in a Gold-Catalysed Synthesis of Functionalised Indenes by the 1,1-Carboalkoxylation of Ynamides

Unique α‐hemiaminal ether gold carbene intermediates were accessed by a gold‐catalysed 1,1‐carboalkoxylation strategy and evolved through a highly selective 1,2‐N‐migration. This skeletal rearrangement gave functionalised indenes, and isotopic labelling confirmed the rare CN bond cleavage of the yn...

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Bibliographic Details
Published in:Chemistry : a European journal 2014-06, Vol.20 (24), p.7262-7266
Main Authors: Adcock, Holly V., Langer, Thomas, Davies, Paul W.
Format: Article
Language:English
Subjects:
Amides - chemistry
Carbenes
Catalysis
Chemistry
Communications
cycloisomerisation
Ethers
Evolution
Gold
Gold - chemistry
Indenes - chemical synthesis
Indenes - chemistry
Labelling
Migration
Molecular Structure
regioselectivity
Selectivity
Stereoisomerism
Strategy
ynamides
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Summary:Unique α‐hemiaminal ether gold carbene intermediates were accessed by a gold‐catalysed 1,1‐carboalkoxylation strategy and evolved through a highly selective 1,2‐N‐migration. This skeletal rearrangement gave functionalised indenes, and isotopic labelling confirmed the rare CN bond cleavage of the ynamide moiety. The effect of substituents on the migration has been explored, and a model is proposed to rationalise the observed selectivity. Migrating nitrogen: A unique α‐hemiaminal ether gold carbene intermediate is invoked in a new gold‐catalysed cycloisomerisation to access functionalised indenes. The use of an ynamide to enforce a 1,1‐carboalkoxylation pathway is followed by a highly selective 1,2‐nitrogen migration for which a selectivity model is proposed (see scheme).
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201403040