Iridium/Acid‐Dual Catalyzed Enantioselective Intramolecular Allylic Dearomatization Reaction of Allylic Alcohol Tethered α‐ and β‐Naphthols

The first catalytic enantioselective intramolecular allylic dearomatization of allylic alcohol tethered α- and β-naphthols has been developed with iridium/acid-dual catalysis. A wide range of polycyclic spiroketones containing vicinal tertiary and quaternary carbon stereocenters were readily prepared in good to high yields with high diastereo- and moderate to excellent enantioselectivities. An unusual anti-Markovnikov Wacker oxidation has also been shown in synthetic transformations.