Straightforward access to the [3.2.2]nonatriene structural framework via intramolecular cyclopropenation/Buchner reaction/Cope rearrangement cascade.

A one-pot cascade process of benzyl enoldiazoacatates, initiated by dirhodium(II)-catalyzed intramolecular cyclopropene formation, occurs via a subsequent Buchner reaction and Cope rearrangement to provide straightforward access to bicyclo[3.2.2]nonatriene derivatives in high yields and selectivities.