Atropurpuran, isolated from the roots of Aconitum hemsleyanum, is a non-alkaloidal diterpene which possesses a unique pentacyclic skeleton that contains an unprecedented tetracyclo[5.3.3.04,9.04,12]tridecane unit. We report herein the formal total synthesis of atropurpuran. The key features of our synthetic route are a high diastereoselective construction of the tri- and tetrasubstituted carbons (i.e., C4, C5, C10, and C20) through an Yb-catalyzed Mukaiyama aldol reaction in an aqueous medium and a one-pot operation including an intramolecular Diels-Alder reaction/ring-closing metathesis to construct the unique pentacyclic skeleton of atropurpuran.