Synthesis of Sulfur-Bridged Polycycles via Pd-Catalyzed Dehydrogenative Cyclization

A general approach to sulfur-bridged polycycles by palladium-catalyzed double C­(sp²)–H bond oxidative cyclization is presented. This protocol afforded diverse sulfur-bridged five-, six-, and seven-membered polycycles in moderate to good yields with a tolerance for a wide variety of functional groups. A sulfide-bridged six-membered pyrene–thienoacene compound was synthesized readily using this method, and excellent performance for photoluminescence quantum yield was observed.