A simple ring current model for describing in-plane aromaticity in pericyclic reactions

Journal of Organic Chemistry

Volumn 64, Issue 6, 1999, Pages 1868-1874

  Morao, Iñaki ^a   Cossío, Fernando P ^a  

^a UNIVERSITY OF THE BASQUE COUNTRY UPV EHU   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

ACETYLENE; AROMATIC COMPOUND; ETHYLENE;

ARTICLE; CALCULATION; CHEMICAL REACTION; GEOMETRY; MODEL; NUCLEAR MAGNETIC RESONANCE; THERMAL ANALYSIS;

EID: 0033583142     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo981862+     Document Type: Article

References (86)

1. Minkin, V. I.; Glukhotsev, M. N.; Simkin, B. Y. Aromaticity and Antiaromaticity: Electronic and Structural Aspects; Wiley : New York, 1994.
2. Schleyer, P. v. R.; Jiao, H. Pure Appl. Chem. 1996, 68, 209 and references therein.
3. See for example: (a) Schleyer, P. v. R.; Freeman, P.; Jiao, H.; Goldfuss, B. Angew. Chem., Int. Ed. Engl. 1995, 34, 337.
4. (b) Dauben, H. J., Jr.; Wilson, J. D.; Laity, J. L. J. Am. Chem. Soc. 1968, 90, 811.
5. See for example: (a) Benson, R. C.; Flygare, W. H. J. Am. Chem. Soc. 1970, 92, 7523.
6. (b) Schmalz, T. G.; Norris, C. L.; Flygare, W. H. J. Am. Chem. Soc. 1973, 95, 7961.
7. Schleyer, P. v. R.; Maerker, C.; Dransfed, A.; Jiao, H.; Hommes N. J. R. v. E. J. Am. Chem. Soc. 1996, 118, 6317.
8. However, this π delocalization can be a consequence of bond equalization of the σ framework. See for example: (a) Hiberty, P. C.; Danovich, D.; Shurki, A.; Shaik, S. J. Am. Chem. Soc. 1995, 117, 7760 and references to previous work therein.
9. (b) Gobbi, A.; Yamaguchi, Y.; Frenking, G.; Schaefer, H. F., III. Chem Phys. Lett. 1995, 244, 27. For a view based on the π framework, see:
10. (c) Baird, N. C. J. Org. Chem. 1986, 51, 3907.
11. (d) Wiberg, K. B.; Nakaji, D.; Breneman, C. J. Am. Chem. Soc. 1989, 11, 4178.
12. (a) Evans, M. G.; Warhurst, E. Trans. Faraday Soc. 1938, 34, 614.
13. (b) Zimmerman, H. E. Acc. Chem. Res. 1971, 4, 272.
14. See for example: (a) Herges, R.; Jiao, H.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1994, 33, 1376.
15. (b) Jiao, H.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl 1993, 32, 1763.
16. (c) Jiao, H.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1995, 34, 334.
17. (d) Jiao, H.; Schleyer, P. v. R. J. Chem. Soc., Perkins Trans. 2 1994, 407.
18. (e) Jiao, H.; Schleyer, P. v. R. J. Am. Chem. Soc. 1995, 117, 11529.
19. Haig, C. W.; Maillon, R. B. Prog. Nucl. Magn. Reson. Spectrosc. 1980, 13, 303 and references therein.
20. Pauling, L. J. Chem. Phys. 1936, 4, 673.
21. (b) London, F. J. Phys. Radium 1937, 8, 397.
22. (c) Pople, J. A. J. Chem. Phys. 1956, 24, 1111.
23. (d) Schneider, W. G.; Bernstein, H. J.; Pople, J. A. J. Am. Chem. Soc. 1958, 80, 3497.
24. Fleischer, U.; Kutzelnigg, W.; Lazzaretti, P.; Muhllenkamp, V. J. Am. Chem. Soc. 1974, 116, 5298.
25. Fowler, P. W.; Steiner, E. J. Phys. Chem. 1997, 101, 1409.
26. Schleyer, P. v. R.; Jiao, H.; Hommes, N. J. R. v. E.; Malkin, V. G.; Malkina, O. L. J. Am. Chem. Soc. 1997, 119, 12669.
27. (a) Chandrasekhar, J.; Jemmis, E. D.; Schleyer, P. v. R. Tetrahedron Lett. 1979, 3707.
28. (b) Dewar, M. J. S. J. Am. Chem. Soc. 1984, 106, 669.
29. (a) Cremer, D. Tetrahedron 1988, 44, 7427.
30. (b) Cremer, D.; Kraka, E. J. Am. Chem. Soc. 1986, 108, 7467.
31. (c) Burk, P.; Abboud, J.-L. M.; Koppel, I. A. J. Phys. Chem. 1996, 100, 6992.
32. (a) Schleyer, P. v. R.; Jiao, H.; Glukhovtsev, M. N.; Chandrasekhar, J.; Kraka, E. J. Am. Chem. Soc. 1994, 116, 10129.
33. (b) McEwen, A. B.; Schleyer, P. v. R. J. Org. Chem. 1986, 51, 4357.
34. Morao, I.; Lecea, B.; Cossío, F. P. J. Org. Chem. 1997, 62, 7033.
35. Gaussian 94, Revision B.2; 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.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; Defrees, D. J.; Baker, J.; Stewart, J. S.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A.; Gaussian, Inc.: Pittsburgh, PA, 1995.
36. (a) Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
37. (b) Lee, C.; Yang, W.; Parr, P. G. Phys. Rev. A 1988, 38, 3098.
38. Frisch, M. J.; Pople, J. A.; Binkley, J. S. J. Chem. Phys. 1994, 80, 3265.
39. (a) Wiest, O.; Black, K. A.; Houk, K. N. J. Am. Chem. Soc. 1994, 116, 10336.
40. (b) Wiest, O.; Houk, K. N.; Black, K. A.; Thomas, B., IV. J. Am Chem. Soc. 1995, 117, 8594.
41. (c) Goldstein, E.; Beno, B.; Houk, H. N. J. Am. Chem. Soc. 1996, 118, 6036.
42. (a) Keith, T. A.; Bader, R. F. W. Chem Phys. Lett. 1993, 210, 223.
43. (b) Keith, T. A.; Bader, R. F. W. Chem. Phys. Lett. 1992, 194, 1.
44. Wolinski, K.; Hilton, J. F.; Pulay, P. J. Am. Chem. Soc. 1990, 112, 8251.
45. Atkins, P. W.; Friedman, R. S. Molecular Quantum Mechanics; Oxford University Press: Oxford, 1997; pp 431-432.
46. Berthelot, M. C. R. Séanc. Acad. Sci. 1866, 62, 905.
47. Schore, N. E. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford, 1991; Vol. 5, pp 1144-1152.
48. Dower, W. V.; Vollhardt, K. P. C. Tetrahedron 1986, 42, 1873.
49. Diercks, R.; Vollhardt, K. P. C. J. Am. Chem. Soc. 1986, 108, 3150.
50. Woodward, R. B.; Hoffmann, R. The Conservation of Orbital Symmetry; Academic Press: New York, 1970.
51. (a) Chase, M. W.; Davies, J. R.; Downey, D. R.; Frurip, R. A.; McDonald, R. A.; Syvervd, A. N. JANAF Thermochemical Tables, Third Ed., J. Phys. Chem. Ref. Data 1985, 14, Suppl. 1.
52. (b) Cox, J. O.; Pilcher, G. Thermochemistry of Organic and Organometallic Compounds; Academic Press: New York, 1970.
53. (a) Bach, R. D.; Wolber, J. W.; Schlegel, H. B. J. Am. Chem. Soc. 1985, 107, 2837.
54. (b) Houk, H. N.; Gandour, R. W.; Rondan, N. G.; Paquette, L. A. J. Am. Chem. Soc. 1979, 101, 6797.
55. Ioffe, A.; Shaik, S. J. Chem. Soc., Perkin Trans 2 1992, 2101.
56. Wagenseller, P. E.; Birney, D. M.; Roy, D. J. Org. Chem. 1995, 60, 2853.
57. Bader, R. F. W. Atoms in Molecules-A Quantum Theory; Clarendon Press: Oxford, 1990; pp 12-52.
58. Pauling, L. The Nature of the Chemical Bond, 3rd ed.; Cornell University Press: Ithaca, 1960; p 224.
59. (a) Cinquinni, M.; Cozzi, F. In Stereoselective Synthesis; Helmcher, G., Hoffmann, R. W., Mulzer, J., Schaumann, E., Eds.; Thieme: Stuttgart, 1996; Vol. 5, pp 2953-2987.
60. (b) Huisgen, R. In 1,3-Dipolar Cycloaddition Chemistry; Padwa, A., Ed.; Wiley: New York, 1984; Vol. 1, p 1.
61. (c) Terao, Y.; Aono, M.; Achiwa, K. Heterocycles 1988, 27, 981.
62. (d) Vedejs, E.; West, F. G. Chem. Rev. 1986, 86, 941.
63. (e) Padwa, A. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford, 1991; Vol. 4, pp 1069-1109.
64. (a) Jones, R. R.; Bergman, R. G. J. Am. Chem. Soc. 1972, 94, 660.
65. (b) Lockhart, T. P.; Bergman, R. G. J. Am. Chem Soc. 1981, 103, 409.
66. (c) Lockhart, T. P.; Commita, P. B.; Bergman, R. G. J. Am. Chem. Soc. 1981, 103, 4082.
67. Enediyne Antibiotics and Antitumor Agents; Borders, D. B., Doyle, T. E., Eds.; Marcel Dekker: New York, 1995.
68. (a) Lindh, R.; Lee, T. J.; Bernhardsson, A.; Persson, B. J.; Karlström, G. J. Am. Chem. Soc. 1995, 117, 7186.
69. (b) Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1991, 113, 1907.
70. (c) Kraka, E.; Cremer, D. J. Am. Chem. Soc. 1994, 116, 4929.
71. (d) Hoffner, J.; Schottelius, M. J.; Feichtinger, D.; Chen, P. J. Am. Chem. Soc. 1998, 120, 376.
72. (e) Lindh, R.; Persson, J. J. Am. Chem. Soc. 1994, 116, 4946.
73. (f) Snyder, J. P. J. Am. Chem. Soc. 1990, 112, 5367.
74. See for example: (a) Nicolaou, K. C.; Ogawa, Y.; Zucarello, G.; Kataoka, H. J. Am. Chem. Soc. 1988, 110, 7247.
75. (b) Nicolaou, K. C.; Zucarello, G.; Ogawa, Y.; Schweiger, E. J.; Kumazawa, T. J. Am. Chem. Soc. 1988, 110, 4866.
76. (c) Schreiber, S. L.; Kiessling, L. L. J. Am. Chem. Soc. 1988, 110, 631.
77. (d) Porco, J. A.; Schoenen, F. J.; Stout, T. J.; Clardy, J.; Schreiber, S. L. J. Am. Chem. Soc. 1990, 112, 7410.
78. (e) Wood, J. L.; Porco, J. A.; Taunton, J.; Lee, A. Y.; Clardy, J.; Schreiber, S. L. J. Am. Chem. Soc. 1992, 114, 5898.
79. (f) Elbaum, D.; Porco, J. A.; Stout, T. J.; Clardy, J.; Schreiber, S. L. J. Am. Chem. Soc. 1995, 117, 211.
80. (g) Magnus, P.; Fortt, S.; Pitterna, T.; Snyder, J. P. J. Am. Chem. Soc. 1990, 112, 4986.
81. Roth, W. R.; Hopf, H.; Horn, C. Chem. Ber. 1994, 127, 1765.
82. rxn = -86.34 kcal/mol. This method is analogous to that used by Schleyer, Houk, Warmuth, et al. for the calculation of the heat of formation of o-benzyne (see ref 43).
83. f value of p-benzyne has an error smaller than that found with a benzyne of much lower biradical character.
84. For recent DFT studies on cyclic enediynes see: (a) Schreiner, P. R. J. Chem. Soc., Chem. Commun. 1998, 483.
85. (b)Schreiner, P. R. J. Am. Chem. Soc. 1998, 120, 4184.
86. One reviewer has indicated that this in-plane aromatic character may be related to the reactant-like nature of the transition structures included in this work. According to his opinion, it would be interesting to scrutinize also reactions with product-like transition structures. We agree with this appreciation, and we are currently investigating this kind of reactions, in which an aromatic ring is generated. These additional studies are underway in our laboratory and will be published separately.