Pd-Catalyzed Intermolecular Carbonylative Dearomatization of Arylamines with Propargylic Acetates for Synthesis of Bridged Polycyclic Lactams.

A new palladium-catalyzed multicomponent dearomatization of arylamines with CO and propargylic acetates for the synthesis of bridged polycyclic lactams is described. This method allows double annulation at the ipso and para positions of the amino group to form four new bonds, three C-C bonds and one C-N bond. DFT calculations and experimental studies indicate that the efficient formation of the allenecarboxanilide intermediate is the key step to achieve the dearomative transformation.