Total Synthesis of (–)‐Perezoperezone through an Intermolecular [5+2] Homodimerization of Hydroxy p‐Quinone

The first copper-catalyzed intermolecular [5+2] homodimerization of hydroxy p-quinone is presented, furnishing bicyclo[3.2.1]octadienone core structures in typically good yields and excellent diastereoselectivities. Applying this synthetic approach enables a concise nine-step total synthesis of (-)-perezoperezone from commercially available 3,5-dimethoxytoluene.