Palladium-Catalyzed Aminomethylative Oppolzer-Type Cyclization of Enynes: Access to Aminomethylated Benzofulvenes.

A novel palladium-catalyzed Oppolzer-type cyclization reaction aided by the aminomethyl cyclopalladated complex has been developed, which provides rapid access to functionalized benzofulvenes with excellent stereoselectivity. The corresponding products can undergo Diels-Alder reaction with maleimides, providing a series of complex polycyclic compounds with excellent regio- and stereoselectivities.