1,2‐<i>N</i>‐Migration in a Gold‐Catalysed Synthesis of Functionalised Indenes by the 1,1‐Carboalkoxylation of Ynamides

Abstract

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.