On the Barriers to Thermally Allowed Reactions and the Elusiveness of Neutral Homoaromaticity

Journal of the American Chemical Society

Volumn 101, Issue 23, 1979, Pages 6797-6802

  Houk, K N ^a   Ruth, Wells Gandour ^a   Strozier, Robert W ^a   Rondan, Nelson G ^a   Paquette, Leo A ^b  

^a LOUISIANA STATE UNIVERSITY   (United States)

^b OHIO STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BENZENE;

ACETYLENE;

EID: 0018784178     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00517a001     Document Type: Article

References (57)

1. Paquette, L.A. Angew. Chem., Int. Ed. Engl. 1978, 17, 106.
2. Berthelot, M. Ann. Chim. Phys. 1866, 9, 445, 469, 481.
3. Justus Liebigs Ann. Chem. 1866, 139, 272.
4. Miller, S.A. “Acetylene: Its Properties, Manufacture, and Uses”, Vol. I; Academic Press: New York, 1965; pp 476-484.
5. Fields, E.K.; Meyerson, S. Tetrahedron Lett. 1967, 571, and references cited therein.
6. Back H.M. Can. J. Chem. 1971, 49, 2199.
7. Altschuler, B.N. Kinet. Katal. 1974, 15, 835. These reactions are endothermic by about 83 and 122 kcal/mol, respectively, but the radical chain mechanism has an overall activation energy of 41.6 kcal/mol.
8. Barkovich, A.J.; Vollhardt, K.P.C. J. Am. Chem. Soc. 1976, 98, 2667.
9. Vollhardt, K.P.C. Acc. Chem. Res. 1977, 10, 1.
10. Barkovich, A.J.; Strauss, E.S.; Vollhardt, K.P.C. J. Am. Chem. Soc. 1977, 99, 8321.
11. Pearson, R.G. “Symmetry Rules for Chemical Reactions” Wiley-Interscience: New York, 1976; p 140.
12. Nutakul, W.; Thummel, R.P.; Taggert, A.D. J. Am. Chem. Soc. 1979, 101, 770.
13. Houk, K.N. Acc. Chem. Res. 1975, 8, 361.
14. For a recent study of contrasting frontier orbital control and charge control behavior within a single structural type, see: Bischof, P.; Gleiter, R.; Taylor, R.T.; Browne, A.R.; Paquette, L.A. J. Org. Chem. 1978, 43, 2391.
15. Browne, A.R.; Paquette, L.A. J. Org. Chem., 1978, 43, 4522.
16. Townshend, R.E.; Ramunni, G.; Segal, G.; Hehre, W.J.; Salem, L. J. Am. Chem. Soc. 1976, 98, 2190.
17. Bingham, R.C.; Dewar, M.J.S.; Lo, D.L. J. Am. Chem. Soc. 1975, 97, 1285.
18. Hehre, W.J.; Lathan, W.A.; Ditchfield, R.; Newton, M.D.; Pople, J.A. QCPE 236. Hehre, W.J.; Stewart, R.F.; Pople, J.A. J. Chem. Phys. 1969, 51, 2657.
19. Mclver, J.W. Acc. Chem. Res. 1974, 7, 72.
20. George, P.; Trachtman, M.; Brett, A.M.; Bock, C.W. Int. J. Quantum Chem. 1977, XII, 61.
21. Not all computational methods predict a similar barrier. For example, extended Huckel calculations predict that benzene should spontaneously fragment to three acetylenes without activation: Bloemer, W.L.; Bruner, B.L. Chem. Phys. Lett. 1972, 17, 452.
22. Wright, J.S. Chem. Phys. Lett. 1970, 6, 476.
23. Wright, J.S. Can.J. Chem. 1975, 53, 549.
24. Dixon, D.A.; Stevens, R.M.; Herschbach, D.R. Discuss. Faraday Soc. 1977, 62, 110.
25. Thompson, D.L.; Suzukawa, H.H., Jr. J. Am. Chem. Soc. 1977, 99, 3614.
26. Caramelia, P.; Houk, K.N.; Domelsmith, L.N. J. Am. Chem. Soc. 1977, 99, 4511.
27. Gordon, M.D.; Fukunaga, T.; Simmons, H.E. J. Am. Chem. Soc. 1976, 98, 8401.
28. Spanget-Larsen, J.; Gleiter, R. Angew. Chem., Int. Ed. Engl. 1978, 17, 441.
29. Evans, M.G.; Polanyi, M. Trans. Faraday Soc. 1938, 34, 11.
30. Evans, M.G.; Warhurst, E. Trans. Faraday Soc. 1938, 34, 614.
31. Evans, M.G. Trans. Faraday Soc. 1939, 35, 824.
32. Wasserman, A. “Diels-Alder Reactions”; Elsevier: Amsterdam, 1965; pp 74-75.
33. Fukui, K. Fortschr. Chem. Forsch. 1970, 15, 1.
34. Bader, R.F.W. Mot. Phys. 1960, 3, 137.
35. Bader, R.F.W. Can. J. Chem. 1962, 40, 1164.
36. Salem, L. Chem. Phys. Lett. 1969, 3, 99.
37. Salem, L.; Wright, J.S. J. Am. Chem. Soc. 1969, 91, 5947.
38. Devaquet, A.; Sevin, A.; Bigot, B. J. Am. Chem. Soc. 1978, 100, 2009.
39. Nagase, S.; Morokuma, K. J. Am. Chem. Soc. 1978, 100, 1666.
40. Strozier, R.W.; Caramelia, P.; Houk, K.N. J. Am. Chem. Soc. 1979, 101, 1340.
41. Firestone, R.F. Tetrahedron 1977, 33, 3009.
42. Houk, K.N. In “Perlcyclic Reactions”, Marchand, A. P., Lehr, R, E., Eds.; Academic Press: New York, 1977; Vol. II, and references cited therein.
43. Winstein, S. J. Am. Chem. Soc. 1959, 81, 6524.
44. Paquette, L.A.; Wallis, T.G.; Kempe, T.; Christoph, G.G.; Springer, J.P.; Clardy, J. J. Am. Chem. Soc. 1977, 99, 6946.
45. Goldstein, M.J. J. Am. Chem. Soc. 1967, 89, 6357.
46. Simmons, H.E.; Fukunaga, T. J. Am. Chem. Soc. 1967, 89, 5208.
47. Hoffmann, R.; Imamura, A.; Zeiss, G.D. J. Am. Chem. Soc. 1967, 89. 5215.
48. Goldstein, M.J.; Hoffmann, R. J. Am. Chem. Soc. 1971, 93, 6193.
49. Bunzli, J.C.; Frost, D.C.; Weiler, L. Tetrahedron Lett. 1973, 1159.
50. Bischof, P.; Bosse, D.; Gleiter, R.; Kukla, J.J.; deMeijere, A.; Paquette, L.A. Chem. Ber. 1975, 108, 1218.
51. Christoph, G.G.; Muthard, J.L.; Paquette, L.A.; Bohm, M.C.; Gleiter, R. J. Am. Chem. Soc. 1978, 100, 7782.
52. Dewar, M.J.S.; de Llano, C. J. Am. Chem. Soc. 1969, 91, 789.
53. Haddon, R.C. J. Am. Chem. Soc. 1975, 97, 3608.
54. Roth, W.R.; Bang, W.B.; Gobel, P.; Sass, R.L.; Turner, R.B.; Yu, A.P. J. Am. Chem. Soc. 1964, 86, 3178.
55. Stevens, E.D.; Kramer, J.D.; Paquette, L.A. J. Org. Chem. 1976, 41, 2266.
56. Allinger, N.L.; Tribble, M.T.; Miller, M.A.; Wertz, D.H. J. Am. Chem. Soc. 1971, 93, 1637.
57. Detty, M.R.; Paquette, L.A. Tetrahedron Lett. 1977, 347.