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The role of oxidation in the biogenesis of alkaloids

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Zusammenfassung

Aminoxide werden als intermediäre Oxydationssubstanzen der Alkaloidbiogenese vorgeschlagen. Verschiedene Beispiele in dem Gebiet der Alkaloide werden erwähnt, um die Hypothese zu erklären.

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References

  1. G. K. Hughes andE. Ritchie, Rev. pure App. Chem.2, 125 (1952).

    CAS  Google Scholar 

  2. G. K. Hughes andE. Ritchie, Rev. pure App. Chem.2, 125 (1952).

    CAS  Google Scholar 

  3. R. F. Dawson, Adv. Enzymology8, 203 (1948).

    CAS  Google Scholar 

  4. F. Challenger, Chem. Rev.36, 315 (1945).

    Article  CAS  Google Scholar 

  5. F. Challenger, Chem. Rev.36, 315 (1945).

    Article  CAS  Google Scholar 

  6. Cf.:S. Kirkwood andL. Marion, Can. J. Chem.29, 30 (1951).

    Article  CAS  Google Scholar 

  7. B. Witkop andS. Goodwin, Exper.8, 377 (1952).

    CAS  Google Scholar 

  8. R. Robinson andS. Sugasawa, J. Chem. Soc.1932, 789.

  9. C. Schoepf andK. Thierfelder, Ann. Chem.497, 22 (1932).

    Article  Google Scholar 

  10. J. Ewing, G. K. Hughes, E. Ritchie, andW. C. Taylor, Nature169, 618 (1952).

    Article  CAS  Google Scholar 

  11. E. Wenkert, Chem. Ind.,1953, 1088.

  12. R. B. Woodward, Nature162, 155 (1948).

    Article  CAS  Google Scholar 

  13. G. K. Hughes andE. Ritchie, Rev. pure App. Chem.2, 125 (1952).

    CAS  Google Scholar 

  14. V. Boekelheide, J. Weinstock, M. F. Grundon, G. L. Sauvage, andE. J. Agnello, J. Amer. Chem. Soc.75, 2550 (1952).

    Article  Google Scholar 

  15. B. Witkop, J. Amer. Chem. Soc.75, 3361 (1953).

    Article  CAS  Google Scholar 

  16. B. Witkop andS. Goodwin, J. Amer. Chem. Soc.75, 3371 (1953).

    Article  CAS  Google Scholar 

  17. One previous suggestion regarding the use of a N-oxide as a biogenetic intermediate was made byRobinson [Chem. Ind.1952, 358] in his interpretation of the origin of the 7-hydroxy group in natural hydroxyindole derivatives. The mechanism of this oxidation, however, was not explained.

  18. M. Polonovski andM. Polonovski, Bull. Soc. chim.39, 1147 (1926), and succeeding papers.

    Google Scholar 

  19. P. J. Scheuer, W. I. Kimoto, andK. Ohinata, J. Amer. Chem. Soc.75, 3029 (1953).

    Article  CAS  Google Scholar 

  20. P. J. Scheuer, W. I. Kimoto, andK. Ohinata, J. Amer. Chem. Soc.75, 3029 (1953).

    Article  CAS  Google Scholar 

  21. O. Diels andE. Fischer, Ber. dtsch. chem. Ges.49, 1721 (1916).

    Article  CAS  Google Scholar 

  22. E. Spaeth, L. Marion, andE. Zajic, Ber. dtsch. chem. Ges.69, 251 (1936).

    Article  Google Scholar 

  23. G. Merling, Amer. Chem. J.216, 343 (1883).

    Google Scholar 

  24. R. Willstätter, Ber. dtsch. chem. Ges.29, 1579, 1637 (1896).

    Google Scholar 

  25. G. R. Clemo andR. Raper, J. Chem. Soc.1933, 644, and preceeding papers.

  26. E. Ochiai, J. Org. Chem.18, 534 (1953).

    Article  CAS  Google Scholar 

  27. G. K. Hughes andE. Ritchie, Rev. pure App. Chem.,2, 125 (1952).

    CAS  Google Scholar 

  28. R. B. Turner andR. B. Woodward, inR. H. F. Manske andH. L. Holmes,The Alkaloids, Vol. III (Academic Press, Inc., Publishers, New York, 1953), p. 54.

    Google Scholar 

  29. R. B. Woodward, Nature162, 155 (1948).

    Article  CAS  Google Scholar 

  30. The oxindole moiety in mitraphylline, rhyncophylline and formosanine (J. W. Cook, R. M. Gailey, andJ. D. London, Chem. Ind.1953, 640) may arise from the oxidation of the indolenine part of XV or from the oxidation and hydration-dehydration of a 3-substituted indole (XXII) [A. Ek, H. Kissman, J. B. Patrick, andB. Witkop, Exper.8, 36 (1952)]. See Formulas XXII and XXIII. Whereas the intermediate XXII requires a slightly different biogenetic elaboration of its amino acid precursors than XIV or XV, an analogy can be drawn with intermediates proposed in the formation of some pyrrocoline bases (E. Wenkert, Chem. Ind.,1953, 1088). Final differentiation between paths XV–XX and XXII–XXIII will have to await total elucidation of structures in the mitragyna series.

    CAS  Google Scholar 

  31. The introduction of N-oxides as biogenetic intermediates precludes the necessity for the use of unusual processes in the formation of gelsemine. In the original scheme [M. S. Gibson andR. Robinson, Chem. Ind.1951, 93.

  32. R. Goutarel, M.-M. Janot, V. Prelog, R. P. A. Sneeden, andW. I. Taylor, Helv. chim. Acta34, 1139 (1951)] both tryptophan and (oxy-)phenylalanine were assumed to act as aldehydes, a proposal now superceded by the route XVI–XXI.

    Article  CAS  Google Scholar 

  33. An alternative suggestion for the origin of the oxindole part of gelsemine, other than the oxidation of the indolenine group in XVI, might be the oxidation and hydration-rearrangement-dehydration of the indole XXIV [Cf.: B. Witkop andA. Ek, J. Amer. Chem. Soc.73, 5664 (1951).

    Article  CAS  Google Scholar 

  34. B. Witkop andJ. B. Patrick, ibid.75, 2572 (1953)].

    Article  CAS  Google Scholar 

  35. R. F. Dawson, Adv. Enzymology8, 203 (1948).

    CAS  Google Scholar 

  36. R. F. Dawson, Adv. Enzymology8, 203 (1948).

    CAS  Google Scholar 

  37. E. Wada andK. Yamasaki, Science117, 152 (1953).

    Article  CAS  Google Scholar 

  38. A. Ek, H. Kissman, J. B. Patrick, andB. Witkop, Exper.8, 36 (1952)]:B. Witkop andA. Ek, J. Amer. Chem. Soc.73, 5664 (1951).

    CAS  Google Scholar 

  39. B. Witkop andJ. B. Patrick, ibid.75, 2572 (1953).

    Article  CAS  Google Scholar 

  40. G. K. Hughes andE. Ritchie, Rev. pure App. Chem.2, 125 (1952).

    CAS  Google Scholar 

  41. E. E. Snell, 2nd Congr. intern. biochim., Chim. biol. V, Symposium metabolisme microbien (Paris)1952, 47.

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Wenkert, E. The role of oxidation in the biogenesis of alkaloids. Experientia 10, 346–350 (1954). https://doi.org/10.1007/BF02160851

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