Divergent C-H Insertion-Cyclization Cascades of N-Allyl Ynamides

Gold carbene reactivity patterns were accessed by ynamide insertion into a C(sp(3))-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(sp(3))-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.