Naphthoquinone-Directed C–H Annulation and Csp3–H Bond Cleavage: One-Pot Synthesis of Tetracyclic Naphthoxazoles

One-pot synthesis of tetracyclic naphthoxazole derivatives from electron-deficient naphthoquinones and alkynes was achieved via Rh­(III)-catalyzed C–H activation and Csp3–H bond cleavage for the first time. This approach proceeds through a tandem cascade process involving substrate tautomerization, C–H activation, oxidative addition, cyclization, and aromatization. In addition, broad substrate scope, simple starting materials, and steric tolerance make this strategy of great practicality.