Construction of Fused Polycyclic Skeletons via Palladium-Catalyzed Dearomatization of Naphthalenes and Benzenes

A novel palladium-catalyzed dearomative cyclization of naphthalenes and benzenes has been accomplished for the expedient construction of fused polycyclic skeletons bearing an all-carbon quaternary center. Excellent functional group tolerance was demonstrated in the reaction of 2,2-phenylnaphthyl acetonitriles, in which the cyano group can serve as a linkage for potential applications. In addition, the challenging dearomatization of benzenes was developed, offering [6,5,6]-carbotricyclic scaffolds that may play a role as an intermediate for the synthesis of fused tricyclic natural products and analogues.