Divergent Syntheses of Fused β‐Naphthol and Indene Scaffolds by Rhodium‐Catalyzed Direct and Decarbonylative Alkyne–Benzocyclobutenone Couplings

Abstract A tunable rhodium‐catalyzed intramolecular alkyne insertion reaction proceeding through the CC cleavage of benzocyclobutenones is described. Selective formation of either the direct or decarbonylative insertion product can be controlled by using different catalytic systems. A variety of fused β‐naphthol and indene scaffolds were obtained in good yields with high functional group tolerance. This work illustrates a divergent approach to synthesize fused‐ring systems by CC activation/functionalization.