Regiocontrolled Annulation of Benzocyclobutenols with Alkynes

A tandem reaction that involves an unprecedented Rh-catalyzed intramolecular annulation of benzocyclobutenols with alkynes and subsequent ZnCl2-promoted dehydration was developed, offering an efficient approach to 2H-furan-, pyran-, and oxepine-fused naphthalenes. Furthermore, the 2H-furan motif may undergo a ring-opening reaction through Fe-catalyzed reductive C–O bond cleavage. As a consequence, the formal intermolecular annulation of 2-hydroxybenzocyclobutenols with alkynes was realized with complete regioselectivity through a two-step protocol.