Abstract
Ab initio and DFT methods were used in combination with various basis sets in order to examine the [4 + 2] Diels–Alder cycloaddition reactions of ethene with 1,3-butadiene, 1,2,4-pentatriene, and 1,2,4,5-hexatetraene with a view to elucidating the role of the allene group in this type of pericyclic reaction. Based on the calculations, the insertion of an allene group decreases the activation energy and increases the exothermal character of the reaction. The decrease is even more marked in the presence of two allene groups, particularly with regard to the reaction enthalpy, which exhibits an additive effect.
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Rodríguez-Otero, J.; Cabaleiro-Lago, E. M. Chem. Eur. J. 2003, 9, 1837.
C. A. Hoeger W. H. Okamura (1985) J. Amer. Chem. Soc. 107 268
Jensen, F. J. Amer. Chem. Soc. 1995, 117, 7487–7492.
Manoharan, M.; Venuvanalingam, P. J. Chem. Soc. Perkin Trans. 1997, 2, 1799.
Hopf, H. Angew. Chem. Intern. Ed. 1972, 11, 419.
Schoen, G.; Hopf, H. Liebigs. Ann. Chem. 1981, p. 165.
Rowley, H.; Steiner, H. Discuss. Faraday Soc. 1951, 10, 198.
Kikuchi, O. Tetrahedron 1971, 27, 2791; Dewar, M. J.; Griffin, A. C.; Kirschner, S. J. Amer. Chem. Soc. 1974, 96, 6225; Townshend, R. E.; Ramunni, G.; Segal, G.; Hehre, W. J.; Salem, L. J. Amer. Chem. Soc. 1976, 98, 2190; Basilevskii, M. V.; Shamov, A. G.; Tikhomirov, V. A. J. Amer. Chem. Soc. 1977, 99, 1369; Burke, L. A.; Leroy, G. Theoret. Chim. Acta 1977, 44, 219; Brown, F. K.; Houk, K. N. Tetrahedron Lett. 1984, 25, 4609; Burke, L. A. Theoret. Chim. Acta 1985, 68, 101; Dewar, M. J. S.; Olivella, S.; Stewart, J. J. P. J. Amer. Chem. Soc. 1986, 108, 5771; Bernardi, F.; Bottoni, A.; Field, M. J.; Guest, M. F.; Hillier, I. H.; Robb, M. A.; Venturini, A. J. Amer. Chem. Soc. 1988, 110, 3050; Bach, R. D.; McDouall, J. J. W.; Schlegel, H. B.; Wolber, G. J. J. Org. Chem. 1989, 54, 2931; Houk, K. N.; Li, Y.; Evanseck, J. D. Angew. Chem. Intern. ed Engl. 1992, 31, 682; Li, Y.; Houk, K. N.; J. Amer. Chem. Soc. 1993, 115, 7478; Goldstein, E.; Beno, B.; Houk, K. N. J. Amer. Chem. Soc. 1996, 118, 6036; Haberl, U.; Wiest, O.; Steckhan, J. Amer. Chem. Soc. 1999, 121, 6730; Sakai, S. J. Phys. Chem. A 2000, 104, 922; Huang, C.; Tsai, L.; Hu, W. J. Phys. Chem. A 2001, 105, 9945, and references cited therein.
Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratmann, R: E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Baboul, A. G.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; W. Gill, P. M.; Johnson, B. G.; Chen, W.; Wong, M. W.; Andres, J. L.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. GAUSSIAN 98; Gaussian, Inc.: Philadelphia, PA, 1998.
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Ferreiro, M.L., Rodríguez-Otero, J. & Cabaleiro-Lago, E.M. Ab Initio and DFT Study of the Influence of the Allene Group on the Diels–Alder Reaction. Structural Chemistry 15, 323–326 (2004). https://doi.org/10.1023/B:STUC.0000026747.11856.1a
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DOI: https://doi.org/10.1023/B:STUC.0000026747.11856.1a