Bridgehead bicyclic unsaturated enamines were prepared by a tandem rhodium-catalyzed C-H bond activation/alkenylation/electrocyclizaton of alkyne-tethered unsaturated imines. These strained bicyclic enamines exhibit unique reactivity: for example, they give N-alkylated products upon treatment with alkylating reagents and undergo double-bond isomerization to alleviate ring strain upon reduction.