Concerted vs stepwise mechanism in 1,3-dipolar cycloaddition of nitrone to ethene, cyclobutadiene, and benzocyclobutadiene. A computational study

Journal of Organic Chemistry

Volumn 65, Issue 19, 2000, Pages 6112-6120

  Di Valentin, Cristiana ^a   Freccero, Mauro ^a   Gandolfi, Remo ^a   Rastelli, Augusto ^b  

^a UNIVERSITY OF PAVIA   (Italy)

^b UNIVERSITY OF MODENA AND REGGIO EMILIA   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

1,3 BUTADIENE; BENZOCYCLOBUTADIENE; CYCLOBUTADIENE; ETHYLENE; NITRONE; UNCLASSIFIED DRUG;

ARTICLE; CALCULATION; CHEMICAL REACTION; CHEMICAL STRUCTURE; ENERGY TRANSFER; ENTROPY;

EID: 0034703407     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo000569i     Document Type: Article

References (80)

1. Tufariello, J. J. Nitrones in 1,3-Dipolar Cycloaddition Chemistry; Padwa, A., Ed.; John Wiley and Sons: New York, 1984; Vol. 2, p 1.
2. Grünanger, P.; Vita Finzi, P. Isoxazoles, Part 1 and 2; Wiley-Interscience: New York, 1991 and 1999.
3. (a) Burdisso, M.; Gamba, A.; Gandolfi, R. Tetrahedron 1988, 44, 3735.
4. (b) Burdisso, M.; Gandolfi, R.; Grünanger, P.; Rastelli, A. J. Org. Chem. 1990, 55, 3427.
5. Rastelli, A.; Gandolfi, R.; Sarzi-Amadè, M. Regioselectivity and Diastereoselectivity in the 1,3-dipolar Cycloadditions of Nitrones with Acrylonitrile and Maleonitrile. The Origin of the Endo/Exo Selectivity. In Advances in Quantum Chemistry; Academic Press: London, 2000; Vol. 36, p 151.
6. Rastelli, A.; Gandolfi, R.; Di Valentin, C., manuscript in preparation.
7. For a computational study on the concerted-stepwise mechanism for cyclobutadiene dimerization: Li, Y.; Houk, K. N. J. Am. Chem. Soc. 1996, 118, 880.
8. For 1,3-dipolar cycloaddition of nitrones to benzocyclobutadiene: Saiko, K.; Watanabe, H.; Sakura, M.; Takahashi, K. Bull. Chem. Soc. Jpn. 1993, 66, 981.
9. Firestone, R. A. J. Org. Chem. 1988, 33, 2285; 1972, 37, 2182; J. Chem. Soc. A 1870, 1570; Tetrahedron 1977, 33, 3009.
10. Firestone, R. A. J. Org. Chem. 1988, 33, 2285; 1972, 37, 2182; J. Chem. Soc. A 1870, 1570; Tetrahedron 1977, 33, 3009.
11. Firestone, R. A. J. Org. Chem. 1988, 33, 2285; 1972, 37, 2182; J. Chem. Soc. A 1870, 1570; Tetrahedron 1977, 33, 3009.
12. Firestone, R. A. J. Org. Chem. 1988, 33, 2285; 1972, 37, 2182; J. Chem. Soc. A 1870, 1570; Tetrahedron 1977, 33, 3009.
13. Huisgen, R. J. Org. Chem. 1968, 33, 2291; 1976, 41, 403.
14. Huisgen, R. J. Org. Chem. 1968, 33, 2291; 1976, 41, 403.
15. (a) Huisgen, R. 1,3-Dipolar Cycloaddition. Introduction, Survey, Mechanism. In 1,3-Dipolar Cycloaddition Chemistry; Padwa, A., Ed.; Wiley-Interscience: New York, 1984; Vol. 1, pp 1-176.
16. (b) Huisgen, R. Pure Appl. Chem. 1981, 53, 171.
17. 1,3-Dipolar Cycloaddition Chemistry, Padwa, A., Ed.; Wiley-Interscience: New York, 1984; Vols. 1 and 2.
18. Houk, K. N.; Gonzales, J.; Li, Y. Acc. Chem. Res. 1995, 28, 81.
19. (a) Huisgen, R. Steric Course and Mechanism of 1,3-Dipolar Cycloadditions. In Advances in Cycloaddition; Curran, D. P., Ed.; JAI Press: London, 1988; Vol. 1, pp 1-31.
20. (b) Quast, H.; Regnat D.; Peters, E.; Peters, K.; von Schnering, H. G. Angew. Chem., Int. Ed. Engl. 1990, 29, 695.
21. (c) Weber, A.; Sauer, J. Tetrahedron Lett. 1998, 39, 807.
22. (d) For a possible example of diradical mechanism see: Baran, J.; Mayr, H. J. Am. Chem. Soc. 1987, 109, 6519; J. Org. Chem. 1989, 54, 5012.
23. (d) For a possible example of diradical mechanism see: Baran, J.; Mayr, H. J. Am. Chem. Soc. 1987, 109, 6519; J. Org. Chem. 1989, 54, 5012.
24. Sauer, J.; Sustmann, R. Angew. Chem., Int. Ed. Engl. 1980, 19, 779.
25. (a) Leroy, G.; Sana, M. Tetrahedron 1975, 31, 2091.
26. (b) Leroy, G.; Nguyen, M. T.; Sana, M. Tetrahedron 1978, 34, 2459.
27. (a) Houk, K. N.; Sims, J. J. Am. Chem. Soc. 1973, 95, 5798.
28. (b) Houk, K. N.; Sims, J.; Duke, R. E.; Strozier, R. W.; George, J. K. J. Am. Chem. Soc. 1973, 95, 7287.
29. (c) Houk, K. N.; Sims, J.; Watts, C. R.; Luskus, T. J. Am. Chem. Soc. 1973, 95, 7301.
30. (d) Liu, J.; Niwayama, S.; You, Y.; Houk, K. N. J. Org. Chem. 1998, 63, 1064.
31. Komornicki, A.; Goddard, J. D., III; Schaefer, H. F. J. Am. Chem. Soc. 1980, 702, 1763.
32. Hiberty, P. C.; Ohanessian, G.; Schlegel, H. B. J. Am. Chem. Soc. 1983, 105, 719.
33. McDouall, J. J. W.; Robb, M. A.; Niazi, U.; Bernardi, F.; Schlegel, B. J. Am. Chem. Soc. 1987, 109, 4642.
34. Pascal, Y. L.; Chanet-Ray, J.; Vessiere, R.; Zeroual, A. Tetrahedron 1992, 35, 7197.
35. Soso, C.; Andzelm, J.; Lee, C.; Blake, J. F.; Chenard, B. L.; Butler, T. W. Int. J. Quantum Chem. 1994, 49, 511.
36. (a) Rastelli, A.; Bagatti, M.; Gandolfi, R. J. Am. Chem. Soc. 1995, 117, 4965.
37. (b) Rastelli, A.; Gandolfi, R.; Sarzi-Amadé M. J. Org. Chem. 1998, 63, 7425.
38. Matsuoka, T.; Harano, K. Tetrahedron 1995, 57, 6451.
39. Sustmann, R.; Sicking, W.; Huisgen, R. J. Am. Chem. Soc. 1995, 117, 9679.
40. (a) Morao, I.; Lecea, B.; Cossìo F. P. J. Org. Chem. 1997, 62, 7033.
41. (b) Cossìo, F. P.; Moras, I.; Jias, H.; Schleyer, P. v. R. J. Am. Chem. Soc. 1999, 121, 6737.
42. Karadakov, P. B.; Cooper, D. L.; Gerratt, J. Theor. Chem. Acc. 1998, 700, 222.
43. Nguyen, M. T.; Chandra, A. K.; Sakai, S.; Morokuma, K. J. Org. Chem. 1999, 64, 65.
44. Su, M.; Lias, H.; Chung, W.; Chu, S. J. Org. Chem. 1999, 64, 6710.
45. Arnaud, R.; Juvin, P.; Vallée, Y. J. Org. Chem. 1999, 64, 8880.
46. Murray, E.; Alvarez-Larena, A.; Piniella, J. F.; Branchadell, V.; Ortuno, R. M. J. Org. Chem. 2000, 65, 388.
47. Hayes, E. F.; Siu, A. Q. S. J. Am. Chem. Soc. 1971, 93, 2091.
48. 2].
49. (a) Wadt, W. R.; Goddard, W. A., III. J. Am. Chem. Soc. 1975, 97, 3004.
50. (b) Harding, L. B.; Goddard, W. A., III. J. Am. Chem. Soc. 1978, 100, 7180.
51. Hiberty, P. C. Israel J. Chem. 1983, 23, 10. Hiberty evaluated the diradical character by expanding MO wave functions into VB wave functions. This amounts to performing HF MO + CI calculations and then projecting the resulting wave function into a basis of VB functions. Then the structure coefficients of a variational VB calculation allows one to determine the structure weights, measuring their relative contribution to the wave function.
52. (a) Harcourt, R. J. Mol. Struct. 1972, 12, 351.
53. (b) Harcourt, R. Tetrahedron 1978, 34, 3125.
54. Page 42 in ref 9a.
55. Walch, S. P.; Goddard, W. A., III. J. Am. Chem. Soc. 1975, 97, 5319.
56. Perkins, M. J. Radical Chemistry; Ellis Horwood: London, 1994; p 68.
57. (a) Balkova, A.; Bartlett, R. J. J. Chem. Phys. 1994, 101, 8972.
58. (b) Metropoulos, A.; Chiu, Y. J. Mol. Struct. 1996, 365, 119.
59. (c) Metropoulos, A.; Chiu, Y. J. Mol. Struct. 1997, 417, 95.
60. (a) Goldstein, E.; Beno, B.; Houk, K. N. J. Am. Chem. Soc. 1996, 118, 6036.
61. (b) Houk, K. N.; Beno, B. R.; Nendel, M.; Black, K.; Yoo, H. Y.; Wilsey, S.; Lee, J. K. THEOCHEM 1997, 388-399, 169.
62. Barone, V.; Arnaud, R. J. Chem. Phys. 1997, 21, 106.
63. (a) Wilsey, S.; Houk, K. N.; Zewail, A. H. J, Am. Chem. Soc. 1999, 121, 4816.
64. (b) Wilsey, S.; Houk, K. N.; Zewail, A. H. J. Am. Chem. Soc. 1999, 121, 5772.
65. 26
66. Chen, W.; Schlegel, H. B. J. Chem. Phys. 1994, 101, 5957.
67. (a) Wittbrodt, J. M.; Schlegel, H. B. J. Chem. Phys. 1996, 705, 6574.
68. (b) Cremer, D.; Kraka, E.; Szalay, P. G. Chem. Phys. Lett. 1998, 292, 97.
69. (a) Yamaguchi, K.; Jensen, F.; Dorigo, A.; Houk, K. N. Chem. Phys. Lett. 1988, 149, 537.
70. (b) Yamanaka, S.; Kawakami, T.; Nagao, H.; Yamaguchi, K. Chem. Phys. Lett. 1994, 231, 25.
71. 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.; 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.; Gill, P. M. W.; Johnson, B. G.; Chen, W.; Wong, M. W.; Andres, J. L.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, revision A.6; Gaussian, Inc.: Pittsburgh, PA, 1998.
72. (a) Tomasi, J.; Persico, M. Chem. Rev. 1997, 94, 2027.
73. (b) Barone, V.; Cossi, M. J. Phys. Chem. A 1998, 102, 1995.
74. Bach, R. D.; Glukhovtsev, M. N.; Gonzales, C.; Marquez, M.; Estevez, C. M.; Baboul, A. G.; Schlegel, H. B. J. Phys. Chem. A 1997, 101, 6092 and references therein.
75. Görling, A.; Trickey, S. B.; Gisdakis, P.; Rösch N. In Topics in Organometallic Chemistry; Brown, J., Hofmann, P., Eds.; Springer: Heidelberg, 1999; Vol. 4, pp 109-163.
76. The solvent effect on the energy of the transition structures, evaluated by the CPCM method at B3LYP/6-31G* level, in dichloromethane and benzene, respectively, is 3-4.3 and -1.1 kcal/mol; 4 -5.6 and -1.3 kcal/mol; 5 -5.7 and -1.5 kcal/mol; endo-9 -4.4 and -0.7 kcal/mol; exo-9 -6.2 and -0.1 kcal/mol; 10a -5.8 and -0.9 kcal/mol; 10b -5.8 and -1.0 kcal/mol; endo-16 -4.8 and -0.4 kcal/mol, exo-16 -6.2 and -1.0 kcal/mol; 17a -6.5 and -0.9 kcal/mol; 17b -5.9 and -0.8 kcal/mol; 17c -6.6 and -1.1 kcal/mol.
77. However, one could argue that B3LYP calculations actually strongly underestimate the energy difference between 4 and 3 and that this error is compensated by increase in energy of 4 induced by spin contamination. Spin contamination removal causes this drawback to emerge.
78. 23 on the potential energy surface of the reaction of nitrone and ethylene with the B3LYP, MP2 and HF methods (always by using a 6-31G* basis set). It is more stable than reactants by ∼2.0 kcal/mol.
79. It should be realized that removal of BSSE would certainly reduce but might even reverse the potential energy gap between reactants and endo-8.
80. The isoxazolidines (i)-13 [(i) conformation] and (o)-13 [(o) conformation] can easily convert into each other by ring flipping and nitrogen inversion: Gandolfi, R.; Grünanger, P. Partially Saturated Polynuclear Isoxazoles, In Grünanger, P.; Vita Finzi, P. Isoxazoles, Part 2; Wiley-Interscience: New York, 1999.