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.