Enantioselective Synthesis of (+)-Auriculatol A

A total synthesis of the grayanane diterpenoid (+)-auriculatol A is reported. The synthesis features a convergent coupling strategy that joins two fragments by a vinylogous Mukaiyama aldol-type reaction and then constructs the 7-membered ring by a nickel-catalyzed eno-late alkenylation. Key findings include the development of a chemoselective Ni-catalyzed intramolecular 1,2-addition to access the bicy-clo[3.2.1]octane fragment and the use of electron-deficient olefin supporting ligands as uniquely effective for the Ni-catalyzed enolate alkenylation.