A biomimetic total synthesis of (+)-intricarene

An asymmetric synthesis of the furanocembrane (−)-bipinnatin J (3a) found in gorgonian corals is described. Treatment of 3a with VO(acac)2-tBuOOH, followed by acetylation, gave acetoxypyranone 15. When 15 was heated in the presence of DBU, it underwent a transannular oxidopyrylium-alkene [5+2] cycloaddition producing the polycyclic diterpene (+)-intricarene 1, isolated from the coral Pseudopterogorgia kallos. The total synthesis of intricarene 1 mimics its most likely biosynthesis via oxidation of bipinnatin J (3a) in vivo.