1-Acetylvinyl Acrylates: New Captodative Olefins Bearing an Internal Probe for the Evaluation of the Relative Reactivity of Captodative against Electron-Deficient Double Bonds in Diels-Alder and Friedel-Crafts Reactions
Keywords:
Captodative olefins, Friedel-Crafts, Diels-Alder cycloaddition, state calculationsAbstract
Abstract. The captodative olefins 1-acetylvinyl esters of methacrylic and trans-crotonic acids, 3a and 3b, have been prepared. The presence of a second double bond in the molecule, acting as an internal probe, allowed us to compare their relative reactivity in Diels-Alder and Friedel-Crafts reactions. The reactivity was evaluated with cyclopentadiene (6) as diene in Diels-Alder cycloadditions, and with furan (9) and thiophene (10) as heteroaromatic Friedel-Crafts substrates. In both processes, the captodative enone double bond proved to be more reactive than that in the acrylic moiety. FMO theory accounted for this chemoselectivity as a consequence of the major π contribution of the enone to the LUMO of these molecules. The slight exo stereoselectivity observed in the cycloaddition to 6 parallels the higher stability of the corresponding transition state, according to the results of B3LYP/6-311G(d,p) calculations.
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References
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4. Sustmann, R.; Tetrahedron Lett. 1971, 2721; Houk, K. N.; Sims, J.; Watts, C. R.; Luskus, L. J.; J. Am. Chem. Soc. 1973, 95, 7301.
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7. García de Alba, O.; Chanona, J.; Delgado, F.; Zepeda, G.; Labarrios, F.; Bates, R. W.; Bott, S.; Juaristi, E.; Tamariz, J.; Anal. Quim. Int. Ed. 1996, 92, 108.
8. Inokuchi, T.; Tanigawa, S.-i.; Torii, S.; J. Org. Chem. 1990, 55, 3958.
9. Aguilar, R.; M.Sc. Dissertation, Escuela Nacional de Ciencias Biológicas, IPN, México, 2000.
10. Olah, G. A.; Krishnamurti, R.; Prakash, G. K. S. In Comprehensive Organic Synthesis; Trost, B. M.; Fleming, I., eds., Pergamon Press: Oxford, 1991, vol. 3, p. 293-339; Bunce, R. A.; Reeves, H. D.; Synth. Commun. 1989, 19, 1109; Yadav, J. S.; Abraham, S.; Reddy, B. V. S.; Sabitha, G.; Synthesis 2001, 2165; Jensen, K. B.; Thorhauge, J.; Hazell, R. G.; Jørgensen, K. A.; Angew. Chem., Int. Ed. 2001, 40, 160.
11. Fleming, I.; Frontier Orbitals and Organic Chemical Reactions, John Wiley & Sons: Chichester, 1976, p. 47-65.
12. García, J. I.; Mayoral, J. A.; Salvatella L.; Acc. Chem. Res. 2000, 33, 658, and references included therein; Yamabe, S.; Minato, T.; J. Org. Chem. 2000, 65, 1830; García, J. I.; Martínez-Merino, V.; Mayoral, J. A.; Salvatella, L.; J. Am. Chem. Soc. 1998, 120, 2415.
13. Loncharich, R. J.; Brown, F. K.; Houk, K. N.; J. Org. Chem. 1989, 54, 1129.
14. Mellor, J. M.; Webb, C. F.; J. Chem. Soc., Perkin Trans. II 1974, 17; Houk, K. N.; Luskus, L. J.; J. Am. Chem. Soc. 1971, 93, 4606; Fox, M. A.; Cardona, R.; Kiwiet, N. J.; J. Org. Chem. 1987, 52, 1469; Boucher, J.-L.; Stella, L.; Tetrahedron 1988, 44, 3595.
15. Kahn, S. D.; Hehre, W. J.; J. Am. Chem. Soc. 1987, 109, 663.
16. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Cioslowski, J.; Stefanov, B. B.; Nanayakkara, A.; Challacombe, M.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres,
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17. Schmidt, M. W.; Baldridge, K. K.; Boatz, J. A.; Elbert, S. T.; Gordon, M. S.; Jensen, J. H.; Koseki, S.; Matsunaga, N.; Nguyen, K. A.; Su, S. J.; Windus, T. L.; Dupui, M.; Montgomery, J. A.; J. Comput. Chem. 1993, 14, 1347.
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