Theoretical Study of the Electronic Effects in the Intramolecular Ketene-Styrene [2+2] Cycloaddition
DOI:
https://doi.org/10.29356/jmcs.v54i4.908Keywords:
B3LYP/6-31 G*, MP2/6-31 G*//B3LYP/6-31 G* calculations Hammett relationship; kinetic control; thermodynamic control; [2 2] cycloaddition.Abstract
DFT (B3LYP/6-31+G*) and post-Hartree-Fock (MP2/6-31+G*//B3LYP/6-31G*) calculations were carried out in order to explain the effect of a remote substituent in the intramolecular ketene-styrene [2+2] cycloaddition of p-substituted 2-methyl-7-arylhepta- 1,6-dien-1-one 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 three-member ring structure and an incipient positive charge development. Kinetic and thermodynamic controls were proposed at B3LYP/6-31+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.
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References
1. Snider, B. B. Chem. Rev. 1998, 88, 793-811.
2. Tidwell, T. T. Ketenes, Wiley, New York, 1995, 486-502 and references therein.
3. Corey, E. J.; Arnold, Z.; Hutton, J. Tetrahedron Lett. 1970, 11, 307-310.
4. Wagner, H. U.; Gompper, R. Tetrahedron Lett. 1970, 11, 2819-2822.
5. Gompper, R. Angew. Chem. Int. Ed. Engl. 1969, 8, 312-327.
6. Ramírez-Galicia, G.; Rubio, M. F.; Jiménez-Cruz, F. J. Mol. Struct. (Theochem) 2006, 773, 53-58.
7. Fleming, I. Frontier Orbitals and Organic Chemical Reactions, Wiley, New York, 1976, pp 110-148.
8. Woodward, R. B.; Hoffmann, R. Angew. Chem. Int. Ed. Engl. 1969, 8, 781-853.
9. Baldwi, J. E.; Kapecki, J. A. J. Am. Chem. Soc. 1970, 92, 4868- 4873.
10. Brady, W. T.; O’Neal, H. R. J. Org. Chem. 1967, 32, 2704-2707.
11. Bèlanger, G.; Lévesque, F.; Pâquet, J.; Barbe, G. J. Org. Chem. 2005, 70, 291-296.
12. Snider, B. B.; Hui, R. A. H. F.; Kulkarni, Y. S. J. Am. Chem. Soc. 1985, 107, 2192-2194.
13. Snider, B. B.; Kulkarni, Y. S. J. Org. Chem. 1987, 52, 307-310.
14. Hammett, L. P. Chem. Rev. 1935, 17, 125-136.
15. Jaffé, H. H. Chem. Rev. 1953, 53, 191-261.
16. Hansch, C.; Leo, A.; Taft, W. Chem. Rev. 1991, 91, 165-195.
17. Hine, J. J. Am. Chem. Soc. 1960, 82, 4877-4880.
18. Charton, M. In Progress in Physical Organic Chemistry Volume
13. Taft R. W., Ed. Wiley, Chichester 1981; 119-251.
19. Roberts, J. D.; Moreland, W. T. J. Am. Chem. Soc. 1953, 75, 2267-2268.
20. Grob, C. A.; Schlageter, M. G. Helv. Chim. Acta 1976, 59, 264-276.
21. http://www.gaussian.com/g_whitepap/thermo/thermo.pdf, accessed in October, 2010.
22. Wang, X.; Houk, K. N. J. Am. Chem. Soc. 1990, 112, 1754-1756.
23. Leach, A. G.; Wang, R.; Wohlhieter, G. E.; Khan, S. I.; Jung, M. E.; Houk, K. N. J. Am. Chem. Soc. 2003, 125, 4271-4278.
24. Connors K. A., in Chemical Kinetics; VCH. Ed., New York, 1990, pp 315-320.
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.; Al-Laham, 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.
26. Becke, A. D. Phys. Rev. A. 1988, 38, 3098-3100.
27. Lee, C. T.; Yang, W. T., Parr, R. G. Phys. Rev. B 1998, 37, 785-789.
28. Scott, A. P.; Radom, L. J. Phys. Chem. 1996, 100, 16502-16513.
29. Moller, C.; Plesset, M. S. Phys. Rev. 1934, 46, 618-622.
30. Binkler, J. S., Pople, J. A. Int. J. Quantum Chemistry 1967, 9, 229-236.
2. Tidwell, T. T. Ketenes, Wiley, New York, 1995, 486-502 and references therein.
3. Corey, E. J.; Arnold, Z.; Hutton, J. Tetrahedron Lett. 1970, 11, 307-310.
4. Wagner, H. U.; Gompper, R. Tetrahedron Lett. 1970, 11, 2819-2822.
5. Gompper, R. Angew. Chem. Int. Ed. Engl. 1969, 8, 312-327.
6. Ramírez-Galicia, G.; Rubio, M. F.; Jiménez-Cruz, F. J. Mol. Struct. (Theochem) 2006, 773, 53-58.
7. Fleming, I. Frontier Orbitals and Organic Chemical Reactions, Wiley, New York, 1976, pp 110-148.
8. Woodward, R. B.; Hoffmann, R. Angew. Chem. Int. Ed. Engl. 1969, 8, 781-853.
9. Baldwi, J. E.; Kapecki, J. A. J. Am. Chem. Soc. 1970, 92, 4868- 4873.
10. Brady, W. T.; O’Neal, H. R. J. Org. Chem. 1967, 32, 2704-2707.
11. Bèlanger, G.; Lévesque, F.; Pâquet, J.; Barbe, G. J. Org. Chem. 2005, 70, 291-296.
12. Snider, B. B.; Hui, R. A. H. F.; Kulkarni, Y. S. J. Am. Chem. Soc. 1985, 107, 2192-2194.
13. Snider, B. B.; Kulkarni, Y. S. J. Org. Chem. 1987, 52, 307-310.
14. Hammett, L. P. Chem. Rev. 1935, 17, 125-136.
15. Jaffé, H. H. Chem. Rev. 1953, 53, 191-261.
16. Hansch, C.; Leo, A.; Taft, W. Chem. Rev. 1991, 91, 165-195.
17. Hine, J. J. Am. Chem. Soc. 1960, 82, 4877-4880.
18. Charton, M. In Progress in Physical Organic Chemistry Volume
13. Taft R. W., Ed. Wiley, Chichester 1981; 119-251.
19. Roberts, J. D.; Moreland, W. T. J. Am. Chem. Soc. 1953, 75, 2267-2268.
20. Grob, C. A.; Schlageter, M. G. Helv. Chim. Acta 1976, 59, 264-276.
21. http://www.gaussian.com/g_whitepap/thermo/thermo.pdf, accessed in October, 2010.
22. Wang, X.; Houk, K. N. J. Am. Chem. Soc. 1990, 112, 1754-1756.
23. Leach, A. G.; Wang, R.; Wohlhieter, G. E.; Khan, S. I.; Jung, M. E.; Houk, K. N. J. Am. Chem. Soc. 2003, 125, 4271-4278.
24. Connors K. A., in Chemical Kinetics; VCH. Ed., New York, 1990, pp 315-320.
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.; Al-Laham, 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.
26. Becke, A. D. Phys. Rev. A. 1988, 38, 3098-3100.
27. Lee, C. T.; Yang, W. T., Parr, R. G. Phys. Rev. B 1998, 37, 785-789.
28. Scott, A. P.; Radom, L. J. Phys. Chem. 1996, 100, 16502-16513.
29. Moller, C.; Plesset, M. S. Phys. Rev. 1934, 46, 618-622.
30. Binkler, J. S., Pople, J. A. Int. J. Quantum Chemistry 1967, 9, 229-236.
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