Skeletal Editing of Azofurans Enabling the Synthesis of Alkoxylated and Aminated γ-Lactams.

A Brønsted acid-catalyzed dearomative furan-to-γ-lactam skeletal editing strategy of azofurans with alcohols or amines is reported, enabling completely regioselective pathway to produce alkoxylated and aminated γ-lactams in generally good yields. Remarkably, despite their disparate nucleophilic profiles, both alcohols and amines individually engage in the skeletal-editing reaction through deliberate switching of the Brønsted acid catalysts, demonstrating a broad scope of substrates with high functional group tolerance. The reaction proceeds under mild, operationally simple conditions, enabling the transformation of planar 2D aromatic furans into 3D γ-lactam with complete regioselectivity.