The Diels−Alder cycloadduct made from 3,5-dibromo-2-pyrone and 2-bromo-styrene was successfullytransformed stereoselectively into a series of novel benzotetracycles via a tandem or sequential Pd-catalyzed coupling−intramolecular Diels−Alder (IMDA) cycloaddition. The resulting polycarbocycles can be readily converted into abicyclo[3.3.1]nonane system upon ozonolysis of the internaldouble bond.