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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.

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