(3aR,7aS)-4-(2-Azidoethyl)-2,2-dimethyl-3a,7a-dihydrobenzo[1,3]dioxole (22) was converted in two steps to trienes23and24, which upon heating underwent intramolecular Diels-Alder reactions to give mixtures of isomeric 11,11-dimethyl-5-oxo-10,12-dioxa-4-azatetracyclo[6.5.2.01,6.09,13]pentadec-14-ene-7-carboxylates25,26and27,28, respectively. These products were separated and identified. For comparison, intermolecular Diels-Alder cycloaddition of diene22with maleic anhydride was carried out. Products of this reaction, 1-(2-azidoethyl)-4,4-dimethyl-3,5,10-trioxatetracyclo[5.5.2.02,6.08,12]tetradec-13-ene-9,11-diones (29and30) were converted to methyl ester analogues of31and32in a two-step sequence. The stereochemical outcome of these cycloadditions is discussed as well as their possible utilization in organic synthesis, especially in total synthesis of some alkaloids.