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 ynamide moiety. The effect of substituents on the migration has been explored, and a model is proposed to rationalise the observed selectivity.
School of Chemistry, University of Birmingham (UK), Fax: (+44) 121-4144403.
Holly V
HV
Adcock
Thomas
T
Langer
Paul W
PW
Davies
D000577:Amides / Q000737:chemistry*; D002384:Catalysis; D006046:Gold / Q000737:chemistry*; D007192:Indenes / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D013237:Stereoisomerism
D000577:Amides; D007192:Indenes; D006046:Gold
carbenes; cycloisomerisation; gold; regioselectivity; ynamides