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The Woodward-Hoffmann Rules in Perspective

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Orbital Symmetry and Reaction Mechanism
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Abstract

In order to appreciate properly the impact of Woodward and Hoffmann’s The Conservation of Orbital Symmetry [1] on contemporary chemical thinking, let us look back to the early nineteen-sixties and recall the state of the art of mechanism elucidation at that time.

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References

  1. R.B. Woodward and R. Hoffmann: Angew. Chern. 81, 797 (1969); Angew. Chern. Internat. Ed. (English) 8, 789 (1969); The Conservation of Orbital Symmetry. Verlag Chemie, Weinheim and Academic Press, New York 1970.

    Google Scholar 

  2. L.P. Hammett: Physical Organic Chemistry. McGraw-Hill, New York: 1st Ed. 1940; 2nd Ed. 1970.

    Google Scholar 

  3. R.P. Bell: Acid and Base Catalysis. Oxford University Press, Oxford 1941.

    Google Scholar 

  4. C.K. Ingold: Structure and Mechanism in Organic Chemistry. Cornell University Press, Ithaca: 1st Ed. 1953; 2nd. Ed. 1969.

    Google Scholar 

  5. L. Melander: Isotope Effects on Reaction Rates. Ronald, New York 1970

    Google Scholar 

  6. E.A. Halevi: Secondary Isotope Effects. In: S.G. Cohen et al. (eds.) Progress in Physical Organic Chemistry. Wiley-Interscience, New York 1963, pp. 109–221.

    Chapter  Google Scholar 

  7. J.E. Leffler and E. Grunwald: Rates and Equilibria of Organic Reactions. Wiley, New York 1963.

    Google Scholar 

  8. W. v.E. Doering and W.R. Roth: Tetrahedron 18, 67 (1962); Angew. Chern. 18, 27 (1962)

    Google Scholar 

  9. See eg pp 32-92 (1st Ed.) and 34-114 (2nd Ed.) of Reference [4] respectively

    Google Scholar 

  10. Nguyen Trong Anh: Les Regles Woodward-Hoffmann. Ediscience, Paris 1970; Die Woodward-Hoffmann Regeln und ihre Anwendung. Verlag Chemie, Weinheim 1972.

    Google Scholar 

  11. Nguyen Trong Anh: Les Regles Woodward-Hoffmann. Ediscience, Paris 1970; Die Woodward-Hoffmann Regeln und ihre Anwendung. Verlag Chemie, Weinheim 1972.

    Google Scholar 

  12. T.L. Gilchrist and R.C. Storr: Organic Reactions and Orbital Symmetry. Cambridge University Press, Cambridge 1972.

    Google Scholar 

  13. R.E. Lehr and A.P. Marchand: Orbital Symmetry - A Problem Solving Approach. Academic Press, New York and London 1972.

    Google Scholar 

  14. A.V. Bellamy: An Introduction to Conservation of Orbital Symmetry - A Programmed Text. Longmans, London 1974.

    Google Scholar 

  15. E. Wigner and E.E. Witmer: Z. Physik 51, 859 (1928).

    Article  CAS  Google Scholar 

  16. F. Hund: Z. Physik 40, 742 (1927); ibid. 42, 93 (1927).

    Article  CAS  Google Scholar 

  17. F. Hund: Z. Physik 40, 742 (1927); ibid. 42, 93 (1927).

    CAS  Google Scholar 

  18. J.E. Lennard-Jones: Trans. Faraday Soc. 51, 668 (1929).

    Article  Google Scholar 

  19. R.S. Mulliken: Rev. Mod. Physics 4, 1 (1932).

    Article  CAS  Google Scholar 

  20. A.D. Walsh: J. Chern. Soc. 1953, 2260 and following papers.

    Google Scholar 

  21. K.E. Shuler: J. Chern. Phys. 21, 624 (1953).

    Article  CAS  Google Scholar 

  22. V.J. Griffing: J. Chern. Phys. 23, 1015 (1955); V.J. Griffing and J.T. Vanderslice: ibid., p l039

    Article  CAS  Google Scholar 

  23. R.F.W. Bader: Canad. J. Chern. 40, 1164 (1962).

    Article  CAS  Google Scholar 

  24. T.F. George and J. Ross: J. Chern. Phys. 55,3851 (1971).

    Article  CAS  Google Scholar 

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

    Google Scholar 

  26. Nguyen Trong Anh: The Use of Aromaticity Rules, Frontier Orbitals and Correlation Diagrams: Some Difficulties and Unsolved Problems. In R. Daudel (ed.) Quantum Theory and Chemical Reactions. Reidel, Dordrecht 1980, pp. 177–89.

    Google Scholar 

  27. I. Fleming: Frontier Orbitals and Organic Chemical Reactions. Wiley, London 1976.

    Google Scholar 

  28. M.G. Evans and E. Warhurst: Trans. Faraday Soc. 34, 614 (1938).

    Article  CAS  Google Scholar 

  29. M.G. Evans: Trans. Faraday Soc. 35, 824 (1939).

    Article  CAS  Google Scholar 

  30. M.J.S. Dewar: Tetrahedron Suppl. 8, 75 (1966); Angew. Chern. 83, 859 (1971); Angew. Chern. Internat. Ed. (English) 10, 761 (1971).

    Article  Google Scholar 

  31. M.J.S. Dewar: Tetrahedron Suppl. 8, 75 (1966); Angew. Chern. 83, 859 (1971); Angew. Chern. Internat. Ed. (English) 10, 761 (1971).

    Article  Google Scholar 

  32. M.J.S. Dewar: Tetrahedron Suppl. 8, 75 (1966); Angew. Chern. 83, 859 (1971); Angew. Chern. Internat. Ed. (English) 10, 761 (1971).

    Article  CAS  Google Scholar 

  33. E. Huckel: Z. Physik 70, 204 (1931).

    Article  CAS  Google Scholar 

  34. See any textbook on MO theory, e g.: a) A. Streitwieser: Molecular Orbital Theory for Organic Chemists. Wiley, New York 1961; b) L. Salem: Molecular Orbital Theory of Conjugated Systems. Benjamin, Reading 1966; c) E. Heilbronner and H. Bock: Das HMO Modell und seine Anwendung, vol. 1. Verlag Chemie, Weinheim 1968; d) H.E. Zimmerman: Quantum Mechanics for Organic Chemists. Academic Press, New York and London 1975

    Google Scholar 

  35. D.P. Craig: J. Chern. Soc. 1959,997.

    Google Scholar 

  36. E. Heilbronner: Tetrahedron Lett. 1964, 1928.

    Google Scholar 

  37. H.E. Zimmerman: a) J. Amer. Chern. Soc. 88, 1563,1566 (1966); b) Accts. Chern. Research 4, 272 (1971); ibid. 5,393 (1972). c) See also Reference [30d, pp 37–41, 113-116, 157-158].

    Article  Google Scholar 

  38. H.E. Zimmerman: a) J. Amer. Chern. Soc. 88, 1563,1566 (1966); b) Accts. Chern. Research 4, 272 (1971); ibid. 5,393 (1972). c) See also Reference [30d, pp 37–41, 113-116, 157-158].

    Article  CAS  Google Scholar 

  39. H.E. Zimmerman: a) J. Amer. Chern. Soc. 88, 1563,1566 (1966); b) Accts. Chern. Research 4, 272 (1971); ibid. 5,393 (1972). c) See also Reference [30d, pp 37–41, 113-116, 157-158].

    CAS  Google Scholar 

  40. See e g D.P. Craig: Aromaticity. In D. Ginsburg (ed.) Non-Benzenoid Aromatic Compounds. Interscience, New York 1959.

    Google Scholar 

  41. J.H. Van Vleck and A. Sherman: Revs. Mod. Phys. 7, 167 (1935).

    Article  Google Scholar 

  42. For a summary of the evidence on the structure and properties of cyclobutadiene, see W.T. Borden and E.R. Davidson: Ann. Revs. Phys. Chern. 30, 134–149 (1979).

    Google Scholar 

  43. K. Fukui, T. Yonezawa and H. Shingu: J. Chern. Phys. 20, 722 (1952).

    Article  CAS  Google Scholar 

  44. K. Fukui, T. Yonezawa, C. Nagata and H. Shingu: J. Chern. Phys. 22, 1433 (1954).

    Article  CAS  Google Scholar 

  45. K. Fukui: Theory of Orientation and Stereoselection. Springer, Heidelberg 1970.

    Google Scholar 

  46. K. Fukui: Accts. Chern. Research 4, 54 (1971) and papers cited therein.

    Google Scholar 

  47. W.Th.A.M. van der Lugt and L.J. Oosterhoff: J. Amer. Chern. Soc. 91, 6042 (1969).

    Article  Google Scholar 

  48. For a critical discussion of the applicability of orbital symmetry considerations to photochemical reactions, see J. Michl: Top. Curro Chern. 46, 1 (1974).

    CAS  Google Scholar 

  49. San-Yan Chu: Tetrahedron 34, 645 (1978).

    Article  CAS  Google Scholar 

  50. Various aspects of this popular approach are presented in G. Klopman (ed.) Chemical Reactivity and Reaction Paths. Wiley, New York 1974.

    Google Scholar 

  51. M.J.S. Dewar and R.C. Dougherty: The PMO Theory of Organic Chemistry. Plenum, New York 1975.

    Book  Google Scholar 

  52. J.A. Berson and I. Salem: J. Amer. Chern. Soc. 94, 8917 (1972); J.A. Berson: Accts. Chern. Research 5, 406 (1971).

    Article  CAS  Google Scholar 

  53. J.A. Berson and I. Salem: J. Amer. Chern. Soc. 94, 8917 (1972); J.A. Berson: Accts. Chern. Research 5, 406 (1971).

    Article  Google Scholar 

  54. S. David, O. Eisenstein, W.J. Hehre, I. Salem and R. Hoffmann: J. Amer. Chern. Soc. 95, 3806 (1973).

    Article  CAS  Google Scholar 

  55. K.N. Houk: Accts. Chern. Research 8, 361 (1975).

    Article  CAS  Google Scholar 

  56. O. Eisenstein, J.M. Lefour, Nguyen Trong Anh and R.F. Hudson: Tetrahedron 33, 523 (1977).

    Article  CAS  Google Scholar 

  57. R.B. Woodward and R. Hoffmann: J. Arner. Chern. Soc. 87, 2046 (1965).

    Article  Google Scholar 

  58. H.C Longuet-Higgins and E.W. Abrahamson: J. Arner. Chern. Soc. 87, 2045 (1965).

    Article  CAS  Google Scholar 

  59. See e g D.M. Silver: J. Arner. Chern. Soc. 96, 5959 (1974) for a discussion of this distinction and its role in the hierarchy of symmetry conservation rules.

    Article  CAS  Google Scholar 

  60. S. Meiboorn and L.C. Snyder: J. Chern. Phys. 52, 3857 (1970).

    Article  Google Scholar 

  61. D.M. Silver and M. Karplus: J. Arner. Chern. Soc. 97,2645 (1975).

    Article  CAS  Google Scholar 

  62. W.G. Dauben,L. Salem and N.J. Turro: Accts. Chern. Research 8, 41 (1975).

    Article  CAS  Google Scholar 

  63. N.J. Turro and P. Lechtken: J. Arner. Chern. Soc. 95, 264 (1973); P. Lechtken, R. Breslow, A.H. Schmidt and N.J. Turro: J. Arner. Chern. Soc. 95,3025 (1973).

    Article  CAS  Google Scholar 

  64. N.J. Turro and P. Lechtken: J. Arner. Chern. Soc. 94, 2886 (1972).

    Article  CAS  Google Scholar 

  65. F.D. Mango and J.H. Schachtschneider: J. Arner. Chern. Soc. 89, 2484 (1967); 94, 2886 (1972).

    Article  Google Scholar 

  66. F.D. Mango and J.H. Schachtschneider: J. Arner. Chern. Soc. 89, 2484 (1967); 94, 2886 (1972).

    Google Scholar 

  67. F. D. Mango: Coord. Chern. Rev. 15, 109–205 (1975) and papers cited therein.

    Article  CAS  Google Scholar 

  68. See in particular: I. Cassar, P.E. Eaton and J. Halpern: J. Arner. Chern. Soc. 94, 3515 (1970); J. Halpern: Accts. Chern. Research 3, 386 (1970). For a full discussion, see Reference [23, p. 401ff.]

    Article  Google Scholar 

  69. See in particular: I. Cassar, P.E. Eaton and J. Halpern: J. Arner. Chern. Soc. 94, 3515 (1970); J. Halpern: Accts. Chern. Research 3, 386 (1970). For a full discussion, see Reference [23, p. 401ff.]

    Article  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  72. I. Salem and J.S. Wright: J. Arner. Chern. Soc. 91, 5947 (1969).

    Article  CAS  Google Scholar 

  73. R.G. Pearson: Accts. Chern. Research 4, 152 (1971).

    Article  CAS  Google Scholar 

  74. E.A. Halevi: Angew. Chern. 88, 664 (1976); Angew. Chern. Internat. Ed. (English) 15,593 (1976).

    Article  CAS  Google Scholar 

  75. E.A. Halevi: Angew. Chern. 88, 664 (1976); Angew. Chern. Internat. Ed. (English) 15,593 (1976).

    Article  Google Scholar 

  76. I. Hargittai and M. Hargittai: Symmetry through the Eyes of a Chemist. Verlag Chernie, Weinheirn 1986.

    Google Scholar 

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Halevi, E.A. (1992). The Woodward-Hoffmann Rules in Perspective. In: Halevi, E.A. (eds) Orbital Symmetry and Reaction Mechanism. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-83568-1_1

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  • DOI: https://doi.org/10.1007/978-3-642-83568-1_1

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