Rhodium(III)-Catalyzed Direct Coupling of Arylphosphine Derivatives with Heterobicyclic Alkenes: A Concise Route to Biarylphosphines and Dibenzophosphole Derivatives

The redox-neutral direct coupling of arylphosphine oxides with heterobicyclic alkenes proceeds smoothly under rhodium­(III) catalysis involving hydroarylation followed by dehydrative aromatization to form biarylphosphine oxides. Related phenylphosphinic and phenylphosphonic esters as well as phenylphosphine sulfides also undergo ortho-arylative coupling. Furthermore, phenylphosphinothioic amides can be transformed to fused dibenzophosphole derivatives through rhodium-catalyzed coupling with heterobicyclic alkenes and successive intramolecular phospha-Friedel–Crafts reaction in a one-pot manner.