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Gold carbene reactivity patterns were accessed by ynamide insertion into a C(sp3)-H bond. A substantial increase in molecular complexity occurred through the cascade polycyclization of N-allyl ynamides to form fused nitrogen-heterocycle scaffolds. Exquisite selectivity was observed despite several competing pathways in an efficient gold-catalyzed synthesis of densely functionalized C(sp3)-rich polycycles and a copper-catalyzed synthesis of fused pyridine derivatives. The respective gold–keteniminium and ketenimine activation pathways have been explored through a structure–reactivity study, and isotopic labeling identified turnover-limiting C-H bond-cleavage in both processes. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]