Catalytic Regiodivergent Dearomatization Reaction of Nitrosocarbonyl Intermediates with ß-Naphthols.

The divergent reactivity of nitrosocarbonyls in oxidative dearomatization of ß-naphthols is reported. In the presence of quinidine catalyst, their reactions with α-unsubstituted ß-naphthols proceeded through the N-center to furnish α-imino-ß-naphthalenones in high yields. Upon exposure to α-substituted ß-naphthols in the presence of copper catalyst, an alteration of regioselectivity was observed to produce α-aminoxylation products. The reaction is scalable, tolerates a wide spectrum of functional groups, and represents a rare example of dearomatization of α-unsubstituted ß-naphthols.