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Cycloadditions and Unimolecular Rearrangements and Eliminations

  • Francis A. Carey
  • Richard J. Sundberg
Part of the Advanced Organic Chemistry book series

Abstract

Other than a few free-radical processes, most of the reactions described to this point have involved polar or easily polarizable reactants. Carbanion reactions, reactions of alkenes with electrophiles, nucleophilic additions to carbonyl groups, metal-promoted and organometallic reactions fall into this category. The reactions to be examined in the present chapter, on the other hand, occur by a reorganization of valence electrons through activated complexes which are not appreciably more polar than the reactants. These reactions, as will be seen, usually proceed through cyclic transition states which contain four, five, or six atoms. Energy sufficient to achieve the transition state is provided by thermal or photochemical excitation of the reacting molecules. Other polar or radical-generating reagents having high chemical potential energy are not usually involved.

Keywords

Maleic Anhydride Vinyl Ether Cycloaddition Reaction Amine Oxide Allylic Alcohol 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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General References

  1. R. B. Woodward and R. Hoffman, The Conservation of Orbital Symmetry, Academic Press, New York (1970).Google Scholar
  2. A. P. Marchand and R. E. Lehr, Editors, Pericyclic Reactions, Vol. I and II, Academic Press, New York (1977).Google Scholar
  3. E. N. Marvell, Thermal Electrocyclic Reactions, Academic Press, New York (1980).Google Scholar
  4. S. J. Rhoads and N. R. Raulins, Org. React., 22, (1975).Google Scholar
  5. E. Block, Reactions of Organosulfur Compounds,Academic Press, New York (1978), Chap. 7.Google Scholar
  6. B. M. Trost and L. S. Melvin, Jr., Sulfur Ylides,Academic Press, New York (1975), Chap. 7.Google Scholar
  7. T. S. Stevens and W. E. Watts, Selected Molecular Rearrangements, Van Nostrand Reinhold, London (1973), Chapter 8.Google Scholar
  8. H.-J. Hansen, in Mechanisms of Molecular Migrations, Vol. 3, B. S. Thyagarajan (ed.), Wiley—Interscience, New York (1971), pp. 177–236.Google Scholar
  9. W. H. Saunders, Jr., and A. F. Cockerill, Mechanisms of Elimination Reactions, Wiley, New York (1973), Chap. VIII.Google Scholar
  10. 1a.
    B. M. Trost, S. A. Godleski, and J. P. Genet, J. Am. Chem. Soc. 100, 3930 (1978).CrossRefGoogle Scholar
  11. b. M. E. Jung and C. A. McCombs, J. Am. Chem. Soc. 100, 5207 (1978).CrossRefGoogle Scholar
  12. c. L. E. Overman and P. J. Jessup, J. Am. Chem. Soc. 100, 5179 (1978).CrossRefGoogle Scholar
  13. d. C. Cupas, W. E. Watts, and P. von R. Schleyer, Tetrahedron Leu. 2503 (1964).Google Scholar
  14. e. T. C. Jain, C. M. Banks, and J. E. McCloskey, Tetrahedron Lett. 841 (1970).Google Scholar
  15. f. G. Büchi and J. E. Powell, Jr., J. Am. Chem. Soc. 89, 4559 (1967).CrossRefGoogle Scholar
  16. g. M. Raban, F. B. Jones, Jr., E. H. Carlson, E. Banucci, and N. A. LeBel, Error! Hyperlink reference not valid Chem. 35, 1497 (1970).Google Scholar
  17. h. H. Yamamoto and H. L. Sham, J. Am. Chem. Soc. 101, 1609 (1979).CrossRefGoogle Scholar
  18. i. H. O. House, T. S. B. Sayer, and C.-C. Yau, Error! Hyperlink reference not valid Chem. 43, 2153 (1978).Google Scholar
  19. j. M. C. Pirrung, J. Am. Chem. Soc. 103, 82 (1981).CrossRefGoogle Scholar
  20. k. M. Sevrin and A. Krief, Tetrahedron Lett. 187 (1978).Google Scholar
  21. l. L. A. Paquette, G. D. Crouse, and A. K. Sharma, J. Am. Chem. Soc. 102, 3972 (1980).CrossRefGoogle Scholar
  22. m. N.-K. Chan and G. Saucy, Error! Hyperlink reference not valid Chem. 42, 3828 (1977).Google Scholar
  23. 2a.
    W. Oppolzer and M. Petrzilka, J. Am. Chem. Soc. 98, 6722 (1976).CrossRefGoogle Scholar
  24. b. A. Padwa and N. Kamigata, J. Am. Chem. Soc. 99, 1871 (1977).CrossRefGoogle Scholar
  25. c. P. A. Jacobi, A. Brownstein, M. Martinelli, and K. Grozinger, J. Am. Chem. Soc. 103, 239 (1981).CrossRefGoogle Scholar
  26. d. H. W. Gschwend, A. O. Lee, and H.-P. Meier, Error! Hyperlink reference not valid Chem. 38, 2169 (1973).Google Scholar
  27. e. T. Kametani, M. Tsubuki, Y. Shiratori, H. Nemoto, M. Ihara, K. Fukumoto, F. Satoh, and H. Inoue, Error! Hyperlink reference not valid Chem. 42, 2672 (1977).Google Scholar
  28. f. J. L. Gras and M. Bertrand, Tetrahedron Lett. 4549 (1979).Google Scholar
  29. 3a.
    K. C. Brannock, A. Bell, R. D. Burpitt, and C. A. Kelly, Error! Hyperlink reference not valid Chem. 29, 801 (1964).Google Scholar
  30. b. K. Ogura, S. Furukawa, and G. Tsuchihashi, J. Am. Chem. Soc. 102, 2125 (1980).CrossRefGoogle Scholar
  31. c. E. Vedejs, M. J. Arco, D. W. Powell, J. M. Renga, and S. P. Singer, Error! Hyperlink reference not valid Chem. 43, 4831 (1978).Google Scholar
  32. d. J. J. Tufariello and J. J. Tegeler, Tetrahedron Lett. 4037 (1976).Google Scholar
  33. e. W. A. Thaler and B. Franzus, Error! Hyperlink reference not valid Chem. 29, 2226 (1964).Google Scholar
  34. f. B. B. Snider, Error! Hyperlink reference not valid Chem. 41, 3061 (1976).Google Scholar
  35. g. L. A. Paquette, Error! Hyperlink reference not valid Chem. 29, 2851 (1964).Google Scholar
  36. h. M. E. Monk and Y. K. Kim, J. Am. Chem. Soc. 86, 2213 (1964).CrossRefGoogle Scholar
  37. i. B. Cazes and S. Julia, Bull. Soc. Chi m. France, 925 (1977).Google Scholar
  38. 4a.
    P. E. Eaton and U. R. Chakraborty, J. Am. Chem. Soc. 100, 3634 (1978).CrossRefGoogle Scholar
  39. b. H. Hogeveen and B. J. Nusse, J. Am. Chem. Soc. 100, 3110 (1978).CrossRefGoogle Scholar
  40. c. T. Oida, S. Tanimoto, T. Sugimoto, and M. Okano, Synthesis, 131 (1980).Google Scholar
  41. d. J. N. Labovitz, C. A. Henrick, and V. L. Corbin, Tetrahedron Lett. 4209 (1975).Google Scholar
  42. e. W. Steglich and L. Zechlin, Chem. Ber. 111, 3939 (1978).CrossRefGoogle Scholar
  43. f. F. D. Lewis and R. J. DeVoe, Error! Hyperlink reference not valid Chem. 45, 948 (1980).Google Scholar
  44. g. S. P. Tanis and K. Nakanishi, J. Am. Chem. Soc. 101, 4398 (1979).CrossRefGoogle Scholar
  45. h. S. Danishefsky, M. P. Prisbylla, and S. Hiner, J. Am. Chem. Soc. 100, 2918 (1978).CrossRefGoogle Scholar
  46. i. T. Hudlicky, F. J. Koszyk, T. M. Kutchan, and J. P. Sheth, Error! Hyperlink reference not valid Chem. 45, 5020 (1980).Google Scholar
  47. 5.
    H. E. Zimmerman, G. L. Grunewald, R. M. Paufler, and M. A. Sherwin, J. Am. Chem. Soc. 91, 2330 (1969).CrossRefGoogle Scholar
  48. 6.
    C. J. Albisetti, N. G. Fisher, M. J. Hogsed, and R. M. Joyce, J. Am. Chem. Soc. 78, 2637 (1956).CrossRefGoogle Scholar
  49. 7.
    N. Shimizu, M. Ishikawa, K. Ishikura, and S. Nishida, J. Am. Chem. Soc. 96, 6456 (1974).CrossRefGoogle Scholar
  50. 8.
    R. Schug and R. Huisgen, Chem. Commun. 60 (1975).Google Scholar
  51. 9.
    W. L. Howard and N. B. Lorette, Org. Synth. V, 25 (1973).Google Scholar
  52. 10.
    S. Danishefsky, M. Hirama, N. Fritsch, and J. Clardy, J. Am. Chem. Soc. 101, 7013 (1979).CrossRefGoogle Scholar
  53. 11.
    D. A. Evans, C. A. Bryan, and C. L. Sims, J. Am. Chem. Soc. 94, 2891 (1972).CrossRefGoogle Scholar
  54. 12.
    J. Wolinsky and R. B. Login, Error! Hyperlink reference not valid Chem. 35, 3205 (1970).Google Scholar
  55. 13.
    C. H. Heathcock and R. A. Badger, Error! Hyperlink reference not valid Chem. 37, 234 (1972).Google Scholar
  56. 14.
    B. J. Arnold, S. M. Mellows, P. G. Sammes, and T. W. Wallace, J. Chem. Soc. Perkin Trans. 1, 401 (1974)CrossRefGoogle Scholar
  57. B. J. Arnold, P. G. Sammes, and T. W. Wallace, J. Chem. Soc. Perkin Trans. 1, 409 (1974).CrossRefGoogle Scholar
  58. 15.
    D. Bichan and M. Winnik, Tetrahedron Lett. 3857 (1974).Google Scholar
  59. 16a.
    R. A. Carboni and R. V. Lindsey, Jr., J. Am. ChemSoc. 81, 4342 (1959).CrossRefGoogle Scholar
  60. b. L. A. Carpino, J. Am. Chem. Soc. 84, 2196 (1962); 85, 2144 (1963).Google Scholar
  61. 17.
    D. L. J. Clive, G. Chittattu, N. J. Curtis, and S. M. Menchen, J. Chem. Soc. Chem. Commun. 7770 (1978).Google Scholar
  62. 18.
    B. W. Metcalf, P. Bey, C. Danzin, M. J. Jung, P. Casara, and J. P. Veveri, J. Am. Chem. Soc. 100, 2551 (1978).CrossRefGoogle Scholar
  63. 19.
    F. M. Schell, J. P. Carter, and C. Wiaux-Zamar, J. Am. Chem. Soc. 100, 2894 (1978).CrossRefGoogle Scholar
  64. 20a.
    D. J. Faulkner and M. R. Peterson, J. Am. Chem. Soc. 95, 553 (1973).CrossRefGoogle Scholar
  65. b. N. A. Le Bel, N. D. Ojha, J. R. Menke, and R. J. Newland, Error! Hyperlink reference not valid Chem. 37, 2896 (1972).Google Scholar
  66. c. G. Büchi and H. Wüest, J. Am. Chem. Soc. 96, 7573 (1974).CrossRefGoogle Scholar
  67. d. C. A. Henrick, F. Schaub, and J. B. Siddall, J. Am. Chem. Soc. 94, 5374 (1972).CrossRefGoogle Scholar
  68. e. R. E. Ireland and R. H. Mueller, J. Am. Chem. Soc. 94, 5897 (1972).CrossRefGoogle Scholar
  69. f. E. J. Corey, R. B. Mitra, and H. Uda, J. Am. Chem. Soc. 86, 485 (1964).CrossRefGoogle Scholar
  70. g. J. E. McMurry and L. C. Blaszczak, Error! Hyperlink reference not valid Chem. 39, 2217 (1974).Google Scholar
  71. h. W. Sucrow, Angew. Chem. Int. Ed. Engl. 7, 629 (1968).Google Scholar
  72. i. O. P. Vig, K. L. Matta, and I. Raj, J. Ind. Chem. Soc. 41, 752 (1964).Google Scholar
  73. j. W. Nagata, S. Hirai, T. Okumura, and K. Kawata, J. Am. Chem. Soc. 90, 1650 (1968).CrossRefGoogle Scholar
  74. k. H. O. House, J. Lubinkowski, and J. J. Good, Error! Hyperlink reference not valid Chem. 40, 86 (1975).Google Scholar
  75. l. L. A. Paquette, G. D. Grouse, and A. K. Sharma, J. Am. Chem. Soc. 102, 3972 (1980).CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 1983

Authors and Affiliations

  • Francis A. Carey
    • 1
  • Richard J. Sundberg
    • 1
  1. 1.University of VirginiaCharlottesvilleUSA

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