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Chemistry of Heterocyclic Compounds

, Volume 48, Issue 2, pp 241–257 | Cite as

Positional selectivity in electrophilic substitution reactions of π-excessive heterocycles (review)

  • L. I. Belen’kiiEmail author
  • N. D. Chuvylkin
  • I. D. Nesterov
Article

Existing experimental data on positional selectivity in electrophilic substitution reactions of π-excessive heterocycles are classified. These data are discussed basing on the results of the authors' quantum-chemical calculations [RHF/6-31G(d), MP2/6-31G(d), and B3LYP/6-31G(d)] of the σ-complexes formed during attack of electrophiles such as H+, Me+, Me3Si+, Br+, NO2 +, MeCO+, and SO3 at the α- and β-positions of furan, thiophene, selenophene, pyrrole and its N-substituted derivatives, N-R-pyrroles (R = Me, t-Bu, SiMe3, Si(i-Pr)3, C6H4(p-NO2), SO2Ph, CHO, CO2Me), and the corresponding α- and β-substituted electrophilic substitution products. The differences in energies of the α-and β-isomers of the σ-complexes characterize the preferred direction of electrophilic attack, while the differences in the energies of the isomeric products make it possible to assess the energy preference of one of them. Analysis of the obtained data demonstrates the effects of the studied heterocycles' structure, the nature of the electrophile, and the thermal and steric factors on the positional selectivity (α/β ratio) in electrophilic substitution reactions of π-excessive five-membered heteroaromatic compounds.

Keywords

furan pyrrole selenophene N-substituted pyrroles thiophene ab initio methods RHF/6-31G(d) and MP2/6-31G(d) B3LYP/6-31G(d) method density functional theory (DFT) electrophilic substitution quantum-chemical calculations 

References

  1. 1.
    G. Marino, Adv. Heterocycl. Chem., 13, 235 (1971).CrossRefGoogle Scholar
  2. 2.
    G. Marino, Khim. Geterotsikl. Soedin., 579 (1973). [Chem. Heterocycl. Compd., 9, 537 (1973)].Google Scholar
  3. 3.
    L. I. Belen'kii, in III International Symposium on Furan Chemistry, Collection of Papers, Smolenice, Czechoslovakia, 1979, p. 4.Google Scholar
  4. 4.
    L. I. Belen'kii, Khim. Geterotsikl. Soedin., 1587 (1980). [Chem. Heterocycl. Compd., 16, 1195 (1980)].Google Scholar
  5. 5.
    P. Linda and G. Marino, J. Chem. Soc., 392 (1968).Google Scholar
  6. 6.
    Z. N. Nazarova, Zh. Obshch. Khim., 24, 575 (1954).Google Scholar
  7. 7.
    Ya. L. Gol'dfarb, Yu. B. Vol'kenshtein, and B. V. Lopatin, Zh. Obshch. Khim., 34, 969 (1964).Google Scholar
  8. 8.
    H. J. Anderson and S.-F. Lee, Can. J. Chem., 43, 409 (1965).CrossRefGoogle Scholar
  9. 9.
    H. J. Anderson and L. C. Hopkins, Can. J. Chem., 42, 1279 (1964).CrossRefGoogle Scholar
  10. 10.
    H. J. Anderson and L. C. Hopkins, Can. J. Chem., 44, 1831 (1966).CrossRefGoogle Scholar
  11. 11.
    H. J. Anderson and C. W. Huang, Can. J. Chem., 45, 897 (1967).CrossRefGoogle Scholar
  12. 12.
    C. E. Loader and H. J. Anderson, Tetrahedron, 25, 3879 (1969).CrossRefGoogle Scholar
  13. 13.
    J. K. Groves, H. J. Anderson, and H. Nagy, Can. J. Chem., 49, 2427 (1971).CrossRefGoogle Scholar
  14. 14.
    C. Jaureguiberry, M. C. Fournier-Zaluski, J. P. Chevallier, and B. Roques, C. R. Acad. Sci., Ser. C, 273, 276 (1971).Google Scholar
  15. 15.
    P. Fournari, M. Farnier, and C. Fournier, Bull. Soc. Chim. Fr., 283 (1972).Google Scholar
  16. 16.
    H. J. Anderson, C. R. Riche, T. G. Costello, C. E. Loader, and G. H. Barnett, Can. J. Chem., 56, 654 (1978).CrossRefGoogle Scholar
  17. 17.
    P. Barker, P. Gendler and H. Rapoport, J. Org. Chem., 43, 4849 (1978).CrossRefGoogle Scholar
  18. 18.
    Ya. L. Gol'dfarb and Yu. B. Vol'kenshtein, Dokl. Akad. Nauk USSR, 128, 536 (1959).Google Scholar
  19. 19.
    S. G. Mairanovskii, N. V. Barashkova, and Yu. B. Vol'kenshtein, Izv. Akad. Nauk USSR, Ser. Khim., 1539 (1965).Google Scholar
  20. 20.
    L. I. Belen'kii, Ya. L. Gol'dfarb, and G. P. Gromova, Izv. Akad. Nauk USSR, Ser. Khim., 2733 (1973).Google Scholar
  21. 21.
    Ya. L. Gol'dfarb, A. P. Yakubov, and L. I. Belen'kii, Izv. Akad. Nauk USSR, Ser. Khim., 185, 941 (1969).Google Scholar
  22. 22.
    L. I. Belen'kii, I. B. Karmanova, and Ya. L. Gol'dfarb, Zh. Org. Khim., 7, 1743 (1971).Google Scholar
  23. 23.
    Ya. L. Gol'dfarb, I. B. Karmanova, Yu. B. Vol'kenshtein, and L. I. Belen'kii, Khim. Geterotsikl. Soedin., 1474 (1978). [Chem. Heterocycl. Compd., 14, 1196 (1978)].Google Scholar
  24. 24.
    Ya. L. Gol'dfarb, E. I. Novikova, and L. I. Belen'kii, Izv. Akad. Nauk USSR, Ser. Khim., 1233 (1971).Google Scholar
  25. 25.
    Ya. L. Gol'dfarb, E. I. Novikova, and L. I. Belen'kii, Izv. Akad. Nauk USSR, Ser. Khim., 2841 (1971).Google Scholar
  26. 26.
    L. I. Belen'kii, E. I. Novikova, and Ya. L. Gol'dfarb, Khim. Geterotsikl. Soedin., 1353 (1971). [Chem. Heterocycl. Compd., 7, 1265 (1971)].Google Scholar
  27. 27.
    D. M. Antonov, L. I. Belen'kii, and S. Gronowitz, J. Heterocycl. Chem., 32, 53 (1995).CrossRefGoogle Scholar
  28. 28.
    G. Hart, D. R. Liljegren, and K. T. Potts, J. Chem. Soc., 4267 (1961).Google Scholar
  29. 29.
    S. Clementi, P. Linda, and G. Marino, J. Chem. Soc., 79 (1971).Google Scholar
  30. 30.
    Tran Quang Minh, F. Mantovani, P. Faller, L. Christiaens, and M. Renson, Bull. Soc. Chim. Fr., 3955 (1972).Google Scholar
  31. 31.
    G. Olah, K. K. Laali, Q. Wang, and G. K. Surya Prakash, Onium Ions, J. Wiley & Sons, New York (1998).Google Scholar
  32. 32.
    H. Meerwein, in: Houben-Weyl Methoden der Organischen Chemie, 4 Aufl., Bd. VI/3, G. Thieme Verlag, Stuttgart (1965), S. 325.Google Scholar
  33. 33.
    J. Goerdeler, in: Houben-Weyl Methoden der Organischen Chemie, 4 Aufl., Bd. IX, G. Thieme Verlag, Stuttgart (1955), S. 174.Google Scholar
  34. 34.
    H. Reinboldt, in: Houben-Weyl Methoden der Organischen Chemie, 4 Aufl., Bd. IX, G. Thieme Verlag, Stuttgart (1955), S. 917.Google Scholar
  35. 35.
    H. Meerwein, E. Battenberg, H. Gold, E. Pfeil, and G Willfang, J. Prakt. Chem., 154, 83 (1939).CrossRefGoogle Scholar
  36. 36.
    L. I. Belen'kii, I. A. Suslov, and N. D. Chuvylkin, Khim. Geterotsikl. Soedin., 38 (2003). [Chem. Heterocycl. Compd., 39, 36 (1971)].Google Scholar
  37. 37.
    L. I. Belen'kii and. A. Abronin, Zh. Org. Khim., 17, 1129 (1981).Google Scholar
  38. 38.
    L. I. Belen'kii, in: 16th International Congress of Heterocyclic Chemistry Abstracts, August 10-15, 1997, Montana State University – Boseman, USA. OP-V-20.Google Scholar
  39. 39.
    L. I. Belen'kii, T. G. Kim, I. A. Suslov, and N. D. Chuvylkin, Izv. Akad. Nauk, Ser. Khim., 837 (2005).Google Scholar
  40. 40.
    A. R. Katritzky and A. F. Pozharskii, Handbook of Heterocyclic Chemistry, 2nd еd., Pergamon, Amsterdam (2000), p. 61.Google Scholar
  41. 41.
    C. F. Candy, R. A. Jones, and P. H. Wright, J. Chem. Soc., 2563 (1970).Google Scholar
  42. 42.
    A. A. Chaikovskaya, Yu. V. Dmitriv, S. P. Ivonin, A. M. Pinchuk, and A. A. Tolmachev, Heteroatom Chem., 16, 599 (2005).CrossRefGoogle Scholar
  43. 43.
    A. A. Chaikovskaya, S. P. Ivonin, Yu. V. Dmitriv, and A. M. Pinchuk, Khim. Geterotsikl. Soedin., 1102 (2005). [Chem. Heterocycl. Compd., 41, 934 (2005)].Google Scholar
  44. 44.
    A. R. Katritzky, K. Suzuki, S. K. Singh, and Hai-Ying He, J. Org. Chem., 68, 5720 (2003).CrossRefGoogle Scholar
  45. 45.
    B. L. Bray, P. H. Mathies, R. Naef, D. R. Solas, Th. T. Tidwell, D. R. Artis, and J. M. Muchowski, J. Org. Chem., 55, 6317 (1990).CrossRefGoogle Scholar
  46. 46.
    A. R. Kennedy, A. I. Khalaf, C. J. Suckling, and R. D. Waigh, Acta Crystallogr., Sect. E: Struct. Rep. Online, 62, o3282 (2006); Chem. Abstr., 146, 263001 (2007).Google Scholar
  47. 47.
    R. C. Foitzik, E. K. Bowen, A. M. Taylor, F. M. Pfeffer, and A. Kaynak, Synth. Met., 157, 924 (2007); Chem. Abstr., 148, 285562 (2008).Google Scholar
  48. 48.
    H. J. Anderson, C. A. Loader, R. X. Xu, N. Le, N. J. Gogan, R. McDonald, and L. G. Edwards, Can. J. Chem., 63, 896 (1985).CrossRefGoogle Scholar
  49. 49.
    R. X. Xu, H. J. Anderson, N. J. Gogan, C. A. Loader, and R. McDonald, Tetrahedron Lett., 22, 4899 (1981).CrossRefGoogle Scholar
  50. 50.
    H. M. Gilow, Y. H. Hong, P. L. Millirons, R. C. Snyder, and W. J. Casteel, Jr., J. Heterocycl. Chem., 23, 1475 (1986).CrossRefGoogle Scholar
  51. 51.
    J. Rokach, P. Hamel, M. Kakushima, and G. M. Smith, Tetrahedron Lett., 22, 4901 (1981).CrossRefGoogle Scholar
  52. 52.
    M. Kakushima, P. Hamel, R. Frenette, and J. Rokach, J. Org. Chem., 48, 3214 (1983).CrossRefGoogle Scholar
  53. 53.
    Ch. Song, D. W. Knight, and M. A. Whatton, Tetrahedron Lett., 45, 9573 (2004).CrossRefGoogle Scholar
  54. 54.
    E. Baum, L. I. Belen'kii, V. G. Kul'nevich, and T. E. Goldovskaya, Khim. Geterotsikl. Soedin., 662 (1982). [Chem. Heterocycl. Compd., 18, 499 (1982)].Google Scholar
  55. 55.
    I. A. Abronin, L. I. Belen'kii, and Ya. L. Gol'dfarb, in: New Trends in Heterocyclic Chemistry, R. B. Mitra, N. R. Ayyangar, V. N. Gogte, R. M. Acheson, and N. Cromwell (editors), Elsevier, Amsterdam (1979), p. 154.Google Scholar
  56. 56.
    M. V. Sigalov and B. A. Trofimov, Zh. Org. Khim., 31, 801 (1995).Google Scholar
  57. 57.
    A. P. Terent'ev and L. A. Yanovskaya, Zh. Obshch. Khim., 19, 538 (1949).Google Scholar
  58. 58.
    A. Mizuno, Y. Kan, H. Fukami, T. Kamei, K. Miyazaki, S. Matsuki, and Y. Oyama, Tetrahedron Lett., 41, 6605 (2000).CrossRefGoogle Scholar
  59. 59.
    T. Janosik, H. Shirani, N. Wahlström, I. Malky, B. Stensland, and J. Bergman, Tetrahedron, 62, 1699 (2006).CrossRefGoogle Scholar
  60. 60.
    M. Renard and L. Hevesi, J. Chem. Soc., Chem. Commun., 688 (1986).Google Scholar
  61. 61.
    M. W. Majchrzak and G. Simchen, Tetrahedron, 42, 1299 (1986).CrossRefGoogle Scholar
  62. 62.
    K. Hrnčariková and D. Végh, Molecules, 8, 536 (2003); Chem. Abstr., 140, 321185 (2004).Google Scholar
  63. 63.
    J. R. Carson and N. M. Davis, J. Org. Chem., 46, 839 (1981).CrossRefGoogle Scholar
  64. 64.
    V. A. Budylin, M. Del K. Pina, and Yu. G. Bundel', Khim. Geterotsikl. Soedin., 562 (1984). [Chem. Heterocycl. Compd., 20, 460 (1984)].Google Scholar
  65. 65.
    J. DeSales, R. Greenhouse, and J. Muchowski, J. Org. Chem., 47, 3668 (1982).CrossRefGoogle Scholar
  66. 66.
    V. A. Budylin, E. D. Matveeva, and A N. Kost, Khim. Geterotsikl. Soedin., 1235 (1980). [Chem. Heterocycl. Compd., 16, 933 (1980)].Google Scholar
  67. 67.
    V. A. Budylin, A. N. Kost, E. D. Matveeva, and V. I. Minkin, Khim. Geterotsikl. Soedin., 68 (1972). [Chem. Heterocycl. Compd., 8, 63 (1972)]Google Scholar
  68. 68.
    V. A. Budylin, M. S. Ermolenko, and A. N. Kost, Khim. Geterotsikl. Soedin., 921 (1978). [Chem. Heterocycl. Compd., 14, 742 (1978)].Google Scholar
  69. 69.
    L. I. Belen'kii, T. G. Kim, I. A. Suslov, and N. D. Chuvylkin, ARKIVOC, xiii, 59 (2003).Google Scholar
  70. 70.
    I. A. Abronin, L. I. Belen'kii, G. M. Zhidomirov, and Ya. L. Gol'dfarb, Zh. Org.. Khim., 17, 1134 (1981).Google Scholar
  71. 71.
    L. I. Belen'kii, N. D. Chuvylkin, T. G. Kim, and I. A. Suslov, in: International Conference "Chemistry Biology Interface: Synergistic New Frontiers", November 21–26, 2004, New Delhi, India, Abstr., IL92.Google Scholar
  72. 72.
    L. I. Belen'kii, N. D. Chuvylkin, A. I. Serykh, and I. A. Suslov, Zh. Org.. Khim., 41, 1362 (2005).Google Scholar
  73. 73.
    L. I. Belen'kii, I. D. Nesterov, and N. D. Chuvylkin, Khim. Geterotsikl. Soedin., 1647 (2006). [Chem. Heterocycl. Compd., 42, 1414 (2006)].Google Scholar
  74. 74.
    L. I. Belen'kii, I. D. Nesterov, and N. D. Chuvylkin, Khim. Geterotsikl. Soedin., 34 (2007). [Chem. Heterocycl. Compd., 43, 28 (2007)].Google Scholar
  75. 75.
    N. D. Chuvylkin, I. D. Nesterov, and L. I. Belen'kii, Izv. Akad. Nauk, Ser. Khim., 1425 (2007).Google Scholar
  76. 76.
    H. Cerfontain, Mechanistic Aspects in Aromatic Sulfonation and Desulfonation, Intersci. Publ., New York (1968).Google Scholar
  77. 77.
    C. W. F. Kort and H. Cerfontain, Rec. Trav. Chim., 88, 860 (1969).CrossRefGoogle Scholar
  78. 78.
    B. V. Salov and A. I. Gershenovich, in: L. I. Belen'kii (editor), Production and Properties of Organic Compounds of Sulfur [in Russian], Khimiya, Moscow (1998), p. 260.Google Scholar
  79. 79.
    L. I. Belen'kii, I. D. Nesterov, and N. D. Chuvylkin, Khim. Geterotsikl. Soedin., 1645 (2008). [Chem. Heterocycl. Compd., 44, 1339 (2008)].Google Scholar
  80. 80.
    L. I. Belen'kii, N. D. Chuvylkin, and I. D. Nesterov, Izv. Akad. Nauk, Ser. Khim., 2163 (2011).Google Scholar
  81. 81.
    M. Speranza, Adv. Heterocycl. Chem., 40, 25 (1986).CrossRefGoogle Scholar
  82. 82.
    M. Speranza, J. Chem. Soc., Chem. Commun., 1177 (1981).Google Scholar
  83. 83.
    C. Angelini, C. Sparapani, and M. Speranza, J. Am. Chem. Soc., 104, 7084 (1982).CrossRefGoogle Scholar
  84. 84.
    L. I. Belen'kii, Adv. Heterocycl. Chem., 99, 143 (2010).CrossRefGoogle Scholar
  85. 85.
    L. I. Belen'kii, G. P. Gromova, B. V. Lichitskii, and M. M. Krayushkin, Khim. Geterotsikl. Soedin., 1477 (1997). [Chem. Heterocycl. Compd., 33, 1276 (1997)].Google Scholar
  86. 86.
    L. I. Belen'kii, I. D. Nesterov, and N. D. Chuvylkin, Khim. Geterotsikl. Soedin., 1801 (2008). [Chem. Heterocycl. Compd., 44, 1460 (2008)].Google Scholar

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© Springer Science+Business Media, Inc. 2012

Authors and Affiliations

  • L. I. Belen’kii
    • 1
    Email author
  • N. D. Chuvylkin
    • 1
  • I. D. Nesterov
    • 1
  1. 1.N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of SciencesMoscowRussia

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