An improved synthesis of exo-heterocyclic dienes like N-substituted 4,5-dimethylene 2-oxazolidinones 1, by a one-step method from diacetyl and isocyanates, was described. This highly convergent synthetic strategy has been successfully used for the preparation of novel (Z)-5-ethylidene-4-methylene analogs 4 in fair yields. Both dienes 1 and 4 undergo efficient addition of symmetric dienophiles in thermal Diels−Alder reactions, inasmuch as they react stereo- and regioselectively with the unsymmetric olefins methyl vinyl ketone (MVK) and methyl propiolate. This regioselectivity was greatly improved by using Lewis acid catalysts (TiCl4, AlCl3). The nitrogen atom of the 2-oxazolidinone ring seems to control the orientation of the dienophile approach. These results have been rationalized in terms of the frontier molecular orbital theory by ab initio calculations. For dienes 4, addition of MVK gave the endo isomer as the major product. Dimerization of dienes 4 was also highly regio-, chemo-, and stereoselective, giving only isomer 17. This reaction furnished a second product, which corresponded to dienes 18 obtained by the [1,5] sigmatropic rearrangement of 4. The structure of the dienes and main products was established by NMR experiments and X-ray diffraction analysis.

One-Step Synthesis and Highly Regio-and Stereoselective Diels-Alder Cycloadditions of Novel exo-2-Oxazolidinone Dienes.-The one-pot reaction between diketones (I) and various isocyanates such as (II) represents a versatile and efficient method, especially for ethylidene derivatives like (IIIc)-(IIIf), where the geometry and position of the exocyclic ethylidene group is completely controlled in the process. Dienes (III) react regio-and stereoselectively with symmetric and unsymmetric dienophiles under thermal or Lewis acid catalyzed conditions. The reactivities and selectivities of the methylene and ethylidene compounds (III) are compared and the results are supported by ab initio calculations of frontier molecular orbitals. The highly chemo-, regio-, and stereoselective dimerization of dienes (IIIc) and (IIIe), yielding only isomer (XIII) as dimeric product, affords a second product (XIV), which is the result of (1,5) sigmatrophic rearrangement of (III). -(MANDAL, A. B.; GOMEZ, A.; TRUJILLO, G.; MENDEZ, F.; JIMENEZ, H. A.; DE JESUS ROSALES, M.; MARTINEZ, R.; DELGADO, F.; TAMARIZ, J.; J.

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