Total Synthesis of ent-Callilongisin B.

The first enantioselective total synthesis of tricyclic diterpenoid callilongisin B, which was isolated from Callicarpa longissima, has been achieved. The synthetic method includes a diastereoselective 1,4-addition and Hosomi-Sakurai allylation followed by Wacker oxidation, intramolecular aldol reaction to construct a six-membered ring, and oxidative dearomatization accompanied by diastereoselective δ-lactonization.