The reactions of cyclopentadiene with alpha-keto-beta,gamma-unsaturated phosphonates or with nitroalkenes proceed through an unsymmetrical bis-pericyclic transition state to give both Diels-Alder and hetero-Diels-Alder cycloadducts. The change in periselectivity of the Lewis acid catalyzed reactions can be qualitatively rationalized by the change in the potential energy surface (PES) landscapes, which ultimately affects the branching ratio of these bis-pericyclic reactions.