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Cycloadditions and Cycloreversions I. [2+2]-Cycloaddition

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Book cover Orbital Symmetry and Reaction Mechanism

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Abstract

It was pointed out in the preceding chapter that correlation diagrams can be read from right to left as easily as from left to right. This is certainly true from the formal viewpoint of orbital symmetry, but does not preclude the need to examine the geometric and energetic consequences of the nuclear motions involved. Thus, for example, the necessity for including a conrotatory (a 2)displacement in the reaction coordinate for the cyclization of s-cis- butadiene (Fig. 5.1) implies that a coordinate with the same irrep has to be incorporated into the reaction coordinate for ring opening of cyclobutene. However the energetic requirements of the nuclear motions involved differ greatly. Internal rotation about the central bond of butadiene — with concomitant conrotation of its terminal methylene groups — is quite facile, whereas the reverse of the same motion in cyclobutene is opposed by a substantial restoring force.

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References

  1. R.A. Moss: Accts. Chern. Research 13,58 (1980); ibid. 22, 15 (1989).

    Article  CAS  Google Scholar 

  2. R.A. Moss: Accts. Chern. Research 13,58 (1980); ibid. 22, 15 (1989).

    CAS  Google Scholar 

  3. R.B. Woodward and R. Hoffmann: The Conservation of Orbital Symmetry. Verlag Chemie, Weinheim and Academic Press, New York 1970.

    Google Scholar 

  4. J. Katriel and E.A. Halevi: Theoret. Chim. Acta. 40, 1 (1975).

    Article  CAS  Google Scholar 

  5. R. Hoffmann: J. Amer. Chern. Soc. 90, 1475 (1968).

    Article  CAS  Google Scholar 

  6. T.A. Albright, J.K. Burdett and M.-H. Whangbo: Orbital Interactions in Chemistry. Wiley, New York 1985.

    Google Scholar 

  7. LR. Gould, N.J. Turro, C. Doubleday, Jr., N.P. Hacker, G.F. Lehr, R.A. Moss, D.P. Cox, W. Guo, R.C. Munjal, L.A. Perez and M. Fedorynski: Tetrahedron 41, 1587 (1985).

    Article  CAS  Google Scholar 

  8. K.N. Houk, N.G. Rondan and J. Mareda: Tetrahedron 41,1555 (1985).

    Article  CAS  Google Scholar 

  9. R.P. Bell: The Proton in Chemistry. Cornell University Press, Ithaca 1959.

    Google Scholar 

  10. E.A. Halevi: Helvet. Chirn. Acta. 58,2136 (1975).

    Article  CAS  Google Scholar 

  11. M.J.S. Dewar and S.Kirschner: J. Arner. Chern. Soc. 96,9246 (1974).

    Google Scholar 

  12. G.A. Segal: J. Arner. Chern. Soc. 96,7892 (1974).

    Article  CAS  Google Scholar 

  13. T. Okada, K. Yamaguchi and T. Fueno: Tetrahedron 30,2293 (1974).

    Article  CAS  Google Scholar 

  14. K.N. Houk: Acc. Chern. Res. 8,361 (1975).

    Article  CAS  Google Scholar 

  15. K. Kraft and G. Koltzenburg: Tetrahedron Letters 1967,4357,4723.

    Google Scholar 

  16. A. Padwa, W. Koehn, J. Massarachia, C.L. Osborn and D.J. Trecker: J. Arner. Chern. Soc. 93,3633 (1971).

    Article  CAS  Google Scholar 

  17. L.E. Gusel’nikov,N.S. Narnetkin and V.M. Volovin: Acc. Chern. Res. 8, 18 (1975) and papers cited therein.

    Article  Google Scholar 

  18. R. Ahlrichs and R. Heinzmann: J. Arner. Chern. Soc. 99,7452 (1977).

    Article  CAS  Google Scholar 

  19. P. Potzinger, B. Reimann and R.S. Roy: Ber. Bunsenges. Phys. Chern. 85, 1119 (1981).

    Article  CAS  Google Scholar 

  20. P.D. Bartlett, L.K. Montgomery and B. Seidel: J. Arner. Chern. Soc. 86,616 (1964).

    Article  CAS  Google Scholar 

  21. L.K. Montgomery, K. Schueller and P.D. Bartlett: J. Arner. Chern. Soc. 86,622 (1964).

    Article  CAS  Google Scholar 

  22. P.D. Bartlett and L.K. Montgomery: J. Arner. Chern. Soc. 86,628 (1964).

    Article  CAS  Google Scholar 

  23. P.D. Bartlett and N.A. Porter: J. Arner. Chern. Soc. 90,5317 (1968).

    Article  CAS  Google Scholar 

  24. P.D. Bartlett: Quart. Revs. Chern. Soc. 24,473 (1970).

    Article  CAS  Google Scholar 

  25. For a thorough discussion of 71’-(J and through-bond-through-space interactions, see R. Gleiter: Angew. Cher. 86, 770 (1974); Angew. Chern. Internat. Ed. (English) 13,696 (1974). See also Reference [5, p. 195ff.].

    Article  CAS  Google Scholar 

  26. For a thorough discussion of 71’-(J and through-bond-through-space interactions, see R. Gleiter: Angew. Cher. 86, 770 (1974); Angew. Chern. Internat. Ed. (English) 13,696 (1974). See also Reference [5, p. 195ff.].

    Article  Google Scholar 

  27. V. Gold (Compiler and Editor): Glossary of Terms Used in Physical Organic Chemistry. Pure and Appl. Chern. 55, 1281ff. (1983).

    Article  CAS  Google Scholar 

  28. J. Leitich: Internat. J. Chern. Kinet. 11,1249 (1980).

    Article  Google Scholar 

  29. A. Padwa and T.J. Blacklock: J. Arner. Chern. Soc. 101,3390 (1979); ibid. 102, 2797 (1980).

    Article  CAS  Google Scholar 

  30. A. Padwa and T.J. Blacklock: J. Arner. Chern. Soc. 101,3390 (1979); ibid. 102, 2797 (1980).

    CAS  Google Scholar 

  31. R. Huisgen: Acc. Chern. Res. 10,117,199 (1977) and references cited therein.

    Article  CAS  Google Scholar 

  32. N.D. Epiotis: Theory of Organic Reactions. Springer, Berlin Heidelberg 1978.

    Book  Google Scholar 

  33. E.A. Halevi: Unpublished calculations.

    Google Scholar 

  34. I. Karle, J. Flippen, R. Huisgen and R. Schug: J. Arner. Chern. Soc. 97, 5285 (1975).

    Article  CAS  Google Scholar 

  35. A. Conan Doyle: The Adventure of the Bruce-Partington Plans.

    Google Scholar 

  36. G. Steiner and R. Huisgen: J. Arner. Chern. Soc. 95, 5056 (1973).

    Article  CAS  Google Scholar 

  37. J. March: Advanced Organic Chemistry, Third edition. Wiley, New York 1985.

    Google Scholar 

  38. R. Huisgen, L.A. Feiler and P.Otto: Chern. Ber. 102,3444 (1969).

    Article  CAS  Google Scholar 

  39. R. Huisgen, L.A. Feiler and G. Binsch: Angew. Chern. 76,892 (1964); Angew. Chern. Internat. Ed. (English) 3,753 (1964).

    Article  CAS  Google Scholar 

  40. R. Huisgen, L.A. Feiler and G. Binsch: Angew. Chern. 76,892 (1964); Angew. Chern. Internat. Ed. (English) 3,753 (1964).

    Article  Google Scholar 

  41. R. Huisgen, L.A. Feiler and G. Binsch: Chern.Ber. 102,3460 (1969).

    Article  CAS  Google Scholar 

  42. R. Montaigne and L. Ghosez: Angew. Chern. 80, 194 (1968); Angew. Chern. Internat. Ed. (English) 7,221 (1968).

    Article  Google Scholar 

  43. R. Montaigne and L. Ghosez: Angew. Chern. 80, 194 (1968); Angew. Chern. Internat. Ed. (English) 7,221 (1968).

    Article  CAS  Google Scholar 

  44. N.S. Isaacs and P. Stanbury: J. Chern. Soc. Perkin II, 1973,166.

    Google Scholar 

  45. J.E. Baldwin and J.A. Kapecki: J. Amer. Chern. Soc. 92,4868 (1970).

    Article  CAS  Google Scholar 

  46. See e g J.E. Leffler and E. Grunwald: Rates and Equilibria of Organic Reactions. Wiley, New York 1963.

    Google Scholar 

  47. R. Huisgen and H. Mayr: Tetrahedron Letters 34, 2965 (1975).

    Article  Google Scholar 

  48. R. Huisgen and H. Mayr: Tetrahedron Letters 34, 2969 (1975).

    Article  Google Scholar 

  49. H.W. Moore: Accts. Chern. Research 12,125 (1979).

    Article  CAS  Google Scholar 

  50. A.H. AI-Husaini and H.W. Moore: J. Org. Chern. 50,2595 (1985).

    Article  Google Scholar 

  51. W. R. Dolbier, Jr. and S.-H. Dai: J. Amer. Chern. Soc. 90, 5028 (1968); S.-H. Dai and W. R. Dolbier, Jr.: J. Amer. Chern. Soc. 94,3946 (1972).

    Article  CAS  Google Scholar 

  52. W. R. Dolbier, Jr. and S.-H. Dai: J. Amer. Chern. Soc. 90, 5028 (1968); S.-H. Dai and W. R. Dolbier, Jr.: J. Amer. Chern. Soc. 94,3946 (1972).

    Article  Google Scholar 

  53. A. Streitwieser, Jr., R.H. Jagow, R.C. Fahey and S. Suzuki: J. Amer. Chern. Soc. 80, 2326 (1958).

    Article  CAS  Google Scholar 

  54. E.A. Halevi: “Secondary Isotope effects” in S.G. Cohen, A. Streitwieser, Jr. and R.W. Taft, Jr. eds. Progress in Physical Organic Chemistry, vol. 1. Wiley-Interscience, New York 1963.

    Google Scholar 

  55. R.J. Crawford and D.M. Cameron: J. Amer. Chern. Soc. 88,2589 (1966).

    Article  CAS  Google Scholar 

  56. J.E. Baldwin and J.A. Kapecki: J. Amer. Chern. Soc. 91,3106 (1969); J. Amer. Chern. Soc. 92,4874 (1970).

    Article  CAS  Google Scholar 

  57. J.E. Baldwin and J.A. Kapecki: J. Amer. Chern. Soc. 91,3106 (1969); J. Amer. Chern. Soc. 92,4874 (1970).

    Article  CAS  Google Scholar 

  58. E. Koerner von Gustorf, D. V. White, J. Leitich and D. Henneberg: Tetrahedron Lett. 1969,3113.

    Google Scholar 

  59. E. Koerner von Gustorf, D. V. White, B. Kim, D. Hess and J. Leitich: J. Org. Chern. 35, 1155 (1970).

    Article  Google Scholar 

  60. E.I. Snyder: J. Org. Chern. 35,4287 (1970).

    Article  CAS  Google Scholar 

  61. N.S. Isaacs and B.G. Hatcher: J. Chern. Soc. Chern. Commun. 1974,593.

    Google Scholar 

  62. R.W. Holder, N.A. Graf, E. Deusler and J.C. Moss: J. Amer. Chern. Soc. 105, 2929, (1983).

    Article  CAS  Google Scholar 

  63. E.A. Halevi and D. Becker: unpublished. Having been denied publication in 1976 on grounds of being “speculative”, the manuscript of this communication was distributed privately to several workers in the field. Its resubmission for publication was postponed sine die after the mechanism outlined in Fig. 6.7 was cited briefly, along with indirect experimental evidence in its support [57].

    Google Scholar 

  64. D. Becker and N.C. Brodsky: J. Chern. Soc. Chern. Cornmun. 1978,237.

    Google Scholar 

  65. R.G. Pearson: Symmetry Rules for Chemical Reactions. Wiley, New York 1976.

    Google Scholar 

  66. R.W. Taft, Jr.: Chapter 13 in M.S. Newman (ed.) Steric Effects in Organic Chemistry. Wiley, New York, 1956.

    Google Scholar 

  67. J. Shorter: Correlation Analysis of Organic Reactivity. Wiley, Chichester 1982.

    Google Scholar 

  68. W.F. Bayne: Tetrahedron Lett. 1970,2263.

    Google Scholar 

  69. T.J. Katz and R. Dessau: J. Amer. Chern. Soc. 85,2172 (1963)

    Article  CAS  Google Scholar 

  70. L.S. Bartell: J. Amer. Chern. Soc. 83, 3567 (1961).

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Department of Chemistry, Technion — Israel Institute of Technology, Technion City, Haifa, 32000, Israel

    E. Amitai Halevi

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  1. Department of Chemistry, Technion — Israel Institute of Technology, Technion City, Haifa, 32000, Israel

    E. Amitai Halevi

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© 1992 Springer-Verlag Berlin Heidelberg

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Halevi, E.A. (1992). Cycloadditions and Cycloreversions I. [2+2]-Cycloaddition. In: Halevi, E.A. (eds) Orbital Symmetry and Reaction Mechanism. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-83568-1_6

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  • DOI: https://doi.org/10.1007/978-3-642-83568-1_6

  • Publisher Name: Springer, Berlin, Heidelberg

  • Print ISBN: 978-3-642-83570-4

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