Enantioselective Total Synthesis of (+)-Fusicoccadiene via Photocatalytic Polyene Isomerization

The fusicoccane diterpenes have amassed interest for their intricate 5-8-5 tricyclic framework and ability to interface with diverse signaling proteins. Herein, we report an enantioselective synthetic platform for the rapid assembly of fusicoccanes where the 5-8-5 motif is prepared via valence bond isomerization of a polyene precursor. A series of regio- and stereoselective modifications to the periphery of this substructure provides entry to diverse fusicoccane congeners. The utility of this strategy is demonstrated with a concise total synthesis of (+)-fusicoccadiene.