(18), respectively, without loss of the olefin configuration. Ethylene tetracarbonitrile (TCE) and N-phenyltriazolinedione (NPTAD) added to these new exocyclic dienes and tetraenes preferentially onto their exo-face. The same face selectivity was observed for the cycloadditions of TCE to the (Z)-and (E)-chlorodienes 9 and 10, thus realizing a case where the kinetic stereoselectivity of the additions is proven not to be governed by the stability of the adducts. The exo-face selectivity of the Diels-Alder additions of dienes grafted onto 7-oxabicyclo [2.2. llheptanes contrasts with the endo-face selectivity reported for a large number of cycloadditions of dienes grafted onto bicyclo [2.2. llheptane skeletons.