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1,2‐ N ‐Migration in a Gold‐Catalysed Synthesis of Functionalised Indenes by the 1,1‐Carboalkoxylation of Ynamides
Author(s) -
Adcock Holly V.,
Langer Thomas,
Davies Paul W.
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201403040
Subject(s) - chemistry , moiety , carbene , hemiaminal , selectivity , ether , cleavage (geology) , stereochemistry , bond cleavage , combinatorial chemistry , medicinal chemistry , organic chemistry , catalysis , geotechnical engineering , fracture (geology) , engineering
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 CN 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.