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Journal of the Mexican Chemical Society
versión impresa ISSN 1870-249X
J. Mex. Chem. Soc vol.54 no.4 Ciudad de México oct./dic. 2010
Article
Theoretical Study of the Electronic Effects in the Intramolecular KeteneStyrene [2+2] Cycloaddition
Manuel Fernando Rubio,1 Federico JiménezCruz2 and Guillermo RamírezGalicia3*
1 Instituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, 04510, Coyoacán, México DF, México.
2 Instituto Mexicano del Petróleo, Eje Central Lázaro Cárdenas 152, San Bartolo Atepehuacan, 07730, México DF, México.
3 Universidad del Papaloapan, División de Estudios de Posgrado, Circuito Central 200, Parque Industrial, 68301, Tuxtepec, Oaxaca, México. email: gramirez@unpa.edu.mx memorgal@gmail.com
Received August 12, 2010.
Accepted September 2, 2010.
Abstract
DFT (B3LYP/631+G*) and postHartreeFock (MP2/631+G*//B3LYP/631G*) calculations were carried out in order to explain the effect of a remote substituent in the intramolecular ketenestyrene [2+2] cycloaddition of psubstituted 2methyl7arylhepta1,6dien1one which produces the bicycle[3.1.1] or the bicycle[3.2.0] heptanones according to Bèlanger experimental results. The transition state geometries were found as an asynchronous process with a threemember ring structure and an incipient positive charge development. Kinetic and thermodynamic controls were proposed at B3LYP/631+G* to determine which product is most likely to form in a competence reaction. In addition, the value of the ρ experimental reaction constant was reproduced, ρ ~ 1.34.
Keywords: B3LYP/631+G*, MP2/631+G*//B3LYP/631+G* calculations Hammett relationship, kinetic control, thermodynamic control, [2+2] cycloaddition.
Resumen
Se realizó un estudio teórico al nivel de teoría DFT (B3LYP/631+G*) y postHartreeFock (MP2/631+G*//B3LYP/631G*) para explicar el efecto del sustituyente remoto en la cicloadición [2+2] intramolecular de cetenaestireno en 2metil7arilhepta1,6dien1ona psustituida la cual produce biciclo[3.1.1] o biciclo[3.2.0] heptanonas de acuerdo a los resultados experimentales de Bèlanger. Se encontró que el estado de transición presenta una geometría de anillo de tres miembros, correspondiente a un estado de transición asincrónico por medio de una carga positiva incipiente. Se propone que la reacción puede ser controlada de forma cinética y termodinámica de acuerdo con los cálculos B3LYP/631+G*. Adicionalmente se reprodujo el valor de la constante de reacción experimental p~ 1.34.
Palabras clave: B3LYP/631+G*, MP2/631+G*//B3LYP/631+G* relaciones tipo Hammett, control cinético, control termodinámico, cicloadición [2+2].
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References
1. Snider, B. B. Chem. Rev. 1998, 88, 793811. [ Links ]
2. Tidwell, T. T. Ketenes, Wiley, New York, 1995, 486502 and references therein. [ Links ]
3. Corey, E. J.; Arnold, Z.; Hutton, J. Tetrahedron Lett. 1970, 11, 307310. [ Links ]
4. Wagner, H. U.; Gompper, R. Tetrahedron Lett. 1970, 11, 28192822. [ Links ]
5. Gompper, R. Angew. Chem. Int. Ed. Engl. 1969, 8, 312327. [ Links ]
6. RamírezGalicia, G.; Rubio, M. F.; JiménezCruz, F. J. Mol. Struct. (Theochem) 2006, 775, 5358. [ Links ]
7. Fleming, I. Frontier Orbitals and Organic Chemical Reactions, Wiley, New York, 1976, pp 110148. [ Links ]
8. Woodward, R. B.; Hoffmann, R. Angew. Chem. Int. Ed. Engl. 1969, 8, 781853. [ Links ]
9. Baldwi, J. E.; Kapecki, J. A. J. Am. Chem. Soc. 1970, 92, 48684873. [ Links ]
10. Brady, W. T.; O'Neal, H. R. J. Org. Chem. 1967, 32, 27042707. [ Links ]
11. Bèlanger, G.; Lévesque, F.; Pâquet, J.; Barbe, G. J. Org. Chem. 2005, 70, 291296. [ Links ]
12. Snider, B. B.; Hui, R. A. H. F.; Kulkarni, Y. S. J. Am. Chem. Soc. 1985, 107, 21922194. [ Links ]
13. Snider, B. B.; Kulkarni, Y. S. J. Org. Chem. 1987, 52, 307310. [ Links ]
14. Hammett, L. P. Chem. Rev. 1935, 17, 125136. [ Links ]
15. Jaffé, H. H. Chem. Rev. 1953, 53, 191261. [ Links ]
16. Hansch, C.; Leo, A.; Taft, W. Chem. Rev. 1991, 91, 165195. [ Links ]
17. Hine, J. J. Am. Chem. Soc. 1960, 82, 48774880. [ Links ]
18. Charton, M. In Progress in Physical Organic Chemistry Volume 13. Taft R. W., Ed. Wiley, Chichester 1981; 119251. [ Links ]
19. Roberts, J. D.; Moreland, W. T. J. Am. Chem. Soc. 1953, 75, 22672268. [ Links ]
20. Grob, C. A.; Schlageter, M. G. Helv. Chim. Acta 1976, 59, 264276. [ Links ]
21. http://www.gaussian.com/g_whitepap/thermo/thermo.pdf, accessed in October, 2010. [ Links ]
22. Wang, X.; Houk, K. N. J. Am. Chem. Soc. 1990, 112, 17541756. [ Links ]
23. Leach, A. G.; Wang, R.; Wohlhieter, G. E.; Khan, S. I.; Jung, M. E.; Houk, K. N. J. Am. Chem. Soc. 2003, 125, 42714278. [ Links ]
24. Connors K. A., in Chemical Kinetics; VCH. Ed., New York, 1990, pp 315320. [ Links ]
25. Gaussian 03, Revision D.01, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery Jr, J. A.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, J. P.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C. ; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J.J.; Zakrzewski, V.G.; Dapprich, S.; Daniels, A.D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A.G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; AlLaham, M. A.; Peng, C.Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian, Inc., Wallingford CT, 2004. [ Links ]
26. Becke, A. D. Phys. Rev. A. 1988, 38, 30983100. [ Links ]
27. Lee, C. T.; Yang, W. T., Parr, R. G. Phys. Rev. B 1998, 37, 785789. [ Links ]
28. Scott, A. P.; Radom, L. J. Phys. Chem. 1996, 100, 1650216513. [ Links ]
29. Moller, C.; Plesset, M. S. Phys. Rev. 1934, 46, 618622. [ Links ]
30. Binkler, J. S., Pople, J. A. Int. J. Quantum Chemistry 1967, 9, 229236. [ Links ]