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Functional Polymers. VII. On the C(3)-Control of Stereochemistry in Asymmetric Reactions Catalyzed by Polymeric Cinchona Alkaloids

Abstract

Asymmetric reactions of dodecanethiol with β-substituted phenyl vinyl ketones were studied using polymeric and monomeric cinchona alkaloids as chiral catalysts. The mode of stereoregulation (C(8), C(9)-control, C(3)-control) varied depending not only on the substituents at C(3) and C(6′) of the alkaloid molecule but also on the β-substituent of the unsaturated systems. The C(3)-control was observed when the steric environments of the enantioface differentiating step were sufficiently crowded (combination of polymer catalyst and bulky β-substituent).

References

  1. 1

    N. Kobayashi and K. Iwai, Macromolecules, 13, 31 (1980).

  2. 2

    N. Kobayashi and K. Iwai, J. Polym. Sci., Polym. Lett. Ed., 18, 417 (1980).

  3. 3

    N. Kobayashi and K. Iwai, Tetrahedron Lett., 21, 2167 (1980).

  4. 4

    G. Berti and A. Marsili, Tetrahedron, 22, 2977 (1966).

  5. 5

    O. Cervinka and O. Belovský, Collect. Czech. Chem. Commun., 32, 3897 (1967).

  6. 6

    G. Marchese, F. Naso, and L. Ronzini, J. Chem. Soc., Chem. Commun., 830 (1974).

  7. 7

    D. Cararet and Z. Welvart, J. Organomet. Chem., 78, 295 (1974).

  8. 8

    L. Meurling, Chemica Scripta, 7, 90 (1975).

  9. 9

    H. Wynberg and R. Helder, Tetrahedron Lett., 4057 (1975).

  10. 10

    H. Pracejus, F. W. Wilcke, and K. Hanemann, J. Prakt. Chem., 319, 219 (1977).

  11. 11

    Y. Okamoto, K. Urakawa, K. Ohta, and H. Yuki, Macromolecules, 18, 923 (1980).

  12. 12

    N. Kobayashi and K. Iwai, J. Polym. Sci., Polym. Chem. Ed., 18, 923 (1980).

  13. 13

    N. Kobayashi and K. Iwai, J. Polym. Sci., Polym. Chem. Ed., 18, 223 (1980).

  14. 14

    T. Fujisawa, K. Hata, and T. Kojima, Synthesis, 38 (1973).

  15. 15

    W. Davey and J. R. Gwilt, J. Chem. Soc., 1008 (1957).

  16. 16

    A. Maccioni and E. Marongiu, Ann. Chim. (Rome), 50, 1806 (1960).

  17. 17

    A. Maccioni and E. Marongiu, Chem. Abstr., 55, 17588d (1961).

  18. 18

    V. Hanzlik and A. Bianchi, Ber., 32, 2282 (1899).

  19. 19

    F. J. Pond and A. S. Shoffstall, J. Am. Chem. Soc., 22, 658 (1900).

  20. 20

    H. Stobe and F. J. Wilson, J. Chem. Soc., 97, 1722 (1910).

  21. 21

    F. Kipnis and J. Ornfelt, J. Am. Chem. Soc., 71, 3554 (1949).

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Kobayashi, N., Iwai, K. Functional Polymers. VII. On the C(3)-Control of Stereochemistry in Asymmetric Reactions Catalyzed by Polymeric Cinchona Alkaloids. Polym J 13, 263–271 (1981). https://doi.org/10.1295/polymj.13.263

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Keywords

  • Asymmetric Reaction
  • Polymer Catalyst
  • Cinchona Alkaloid
  • Stereochemistry
  • Thiol
  • α,β-Unsaturated Compound

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