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

Abstract 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.