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C(14)-substituted corticosteroids. some D ring transformations in the compound S series

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Zusammenfassung

Eine Anzahl am D-Ring substituierter Derivate von Reichsteins Verbindung S wurde als Modellverbindungen in der Synthese neuer Corticosteroide hergestellt. Die beschriebenen Strukturtypen schliessen Dehydroverbindungen, Epoxyde, Halogenhydrine und ein Glykol ein.

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References

  1. J. Fried et al., J. Amer. chem. Soc.75, 2273 (1953);76, 1455 (1954);77, 1068 (1955);77, 4181 (1955).

    Article  CAS  Google Scholar 

  2. A. Nobile et al., J. Amer. chem. Soc.77, 4184 (1955).

    Article  CAS  Google Scholar 

  3. R. F. Hirschmann, R. Miller, R. E. Beyler, L. H. Sarett, andM. Tishler, J. Amer. chem. Soc.77, 3166 (1955).

    Article  CAS  Google Scholar 

  4. J. A. Hogg et al., J. Amer. chem. Soc.77, 4438 (1955).

    Article  CAS  Google Scholar 

  5. E. Vischer, Ch. Meystre, andA. Wettstein, Helv. chim. Acta38, 835 (1955).

    Article  CAS  Google Scholar 

  6. E. J. Agnello, B. M. Bloom, andG. D. Laubach, J. Amer. chem. Soc.77, 4684 (1955); Abstracts of 128th Meeting, Amer. Chem. Soc., Minneapolis, Minn., September 11–16, 1955, p. 50.

    Article  CAS  Google Scholar 

  7. H. C. Murray andD. H. Peterson, U.S. 2,602,769, July 8, 1952; U.S. 2,673,866, March 30, 1954.

  8. P. D. Meister et al., Abstracts of Papers, 123rd Amer. Chem. Soc. Meeting, Los Angeles, Calif., March 15–19, 1953, p. 5C.

  9. A. F. St. André, H. B. MacPhillamy, J. A. Nelson, A. C. Shabica, andC. R. Scholz, J. Amer. chem. Soc.74, 5506 (1952).

    Article  Google Scholar 

  10. Activated 14α-hydroxyl functions are known to dehydrate readily toward C(15) under mild acidic conditions.Cf. G. D. Laubach, E. C. Schreiber, E. J. Agnello, E. N. Lightfoot, andK. J. Brunings, J. Amer. chem. Soc.75, 1514 (1953).

    Article  CAS  Google Scholar 

  11. N. L. McNiven, J. Amer. chem. Soc.76, 1725 (1954).

    Article  CAS  Google Scholar 

  12. A. Zürcher, H. Heusser, O. Jeger, andP. Geistlich, Helv. chim. Acta37, 1562 (1954).

    Article  Google Scholar 

  13. Private communication from Dr.Howard Ringold of Syntex, S.A.

  14. E. J. Corey, J. Amer. chem. Soc.76, 175 (1954).

    Article  CAS  Google Scholar 

  15. H. M. E. Cardwell andS. Smith, J. chem. Soc.1954, 2012.

  16. C. J. W. Brooks andJ. K. Norymberski, Biochem. J.55, 371 (1953).

    Article  CAS  Google Scholar 

  17. A. F. St. André, H. B. MacPhillamy, J. A. Nelson, A. C. Shabica, andC. R. Scholz, J. Amer. chem. Soc.74, 5506 (1952).

    Article  Google Scholar 

  18. The formation of identical epoxidation products from highly substituted olefins using either peracids or chromate oxidizing agents has been observed frequently [cf. H. Reich andA. Lardon, Helv. chim. Acta30, 329 (1947).

    Article  CAS  Google Scholar 

  19. C. W. Shoppee, Helv. chim. Acta30, 766 (1947)]. A recent example in the terpene series is cited byJ. D. Johnston andF. S. Spring, J. chem. Soc.1954, 1556.

    Article  CAS  Google Scholar 

  20. Preferential α-face attack by bulky reagents in the steroid series is thoroughly documented.Cf. L. F. Fieser, Exper.6, 312 (1950).

    CAS  Google Scholar 

  21. Pl. A. Plattner et al., Helv. chim. Acta29, 2023 (1946).

    Article  CAS  Google Scholar 

  22. T. F. Gallagher andT. H. Kritchevsky, J. Amer. chem. Soc.72, 882 (1950).

    Article  CAS  Google Scholar 

  23. G. H. Alt andD. H. R. Barton, J. chem. Soc.1954, 1356.

  24. P. Bladon, J. chem. Soc.1954, 736.

  25. Unsuccessful attempts were made to cleave the epoxide linkage in VII with boiling acetic acid [J. Pataki, G. Rosenkranz, andC. Djerassi, J. Amer. chem. Soc.73, 5375 (1951).

    Article  CAS  Google Scholar 

  26. A. Forst andPl. A. Plattner, Helv. chim. Acta32, 275 (1949)], thiocyanic acid [E. E. van Tamelen, J. Amer. chem. Soc.73, 3444 (1951)], pyridine hydrobromide [P. N. Chakravorty andR. H. Levin, J. Amer. Chem. Soc.64, 2317 (1942)], thiourea andp-toluenesulfonic acid [L. C. King andJ. A. Campell, J. Amer. chem. Soc.71, 3556 (1949)], magnesium bromide etherate [W. E. Bachmann, J. P. Horwitz, andR. J. Warzynski, J. Amer. chem. Soc.75, 3268 (1953).

    Article  Google Scholar 

  27. R. B. Turner, J. Amer. chem. Soc.75, 3484 (1953)], and trichloroacetic acid in benzene [A. Forst andR. Scotoni, Jr., Helv. chim. Acta36, 1410 (1953)].

    Article  CAS  Google Scholar 

  28. Inter al.,S. A. Julia andH. Heusser, Helv. chim. Acta35, 2080 (1952).

    Article  CAS  Google Scholar 

  29. More vigorous reaction conditions resulted in the formation of III as the predominant product. The reduction of steroid epoxides to the parent olefins by hydriodic acid has been previously observed. [J. Fried et al., J. Amer. chem. Soc.75, 2273 (1953);

    Article  CAS  Google Scholar 

  30. P. L. Julian et al., J. Amer. chem. Soc.72, 5145 (1950).

    Article  CAS  Google Scholar 

  31. L. B. Barkley, M. W. Farrar, W. S. Knowles, andH. Raffelson, J. Amer. Chem. Soc.76, 5017 (1953).

    Article  Google Scholar 

  32. J. Schmidlin andA. Wettstein, Helv. chim. Acta36, 1241 (1953).

    Article  CAS  Google Scholar 

  33. G. P. Mueller, R. E. Stobaugh, andR. S. Winniford, J. Amer. chem. Soc.75, 4888 (1953).

    Article  CAS  Google Scholar 

  34. J. W. Cornforth, J. M. Osbond, andG. H. Phillips, J. chem. Soc.1954, 907.

  35. L. F. Fieser andX. A. Dominguez, J. Amer. chem. Soc.75, 1704 (1953).

    Article  CAS  Google Scholar 

  36. J. Fried et al., J. Amer. chem. Soc.75, 2273 (1953).

    Article  CAS  Google Scholar 

  37. J. Fried et al., J. Amer. chem. Soc.75, 2273 (1953).

    Article  CAS  Google Scholar 

  38. G. H. Ott andT. Reichstein, Helv. chim. Acta26, 1799 (1943).

    Article  CAS  Google Scholar 

  39. G. I. Poos, G. E. Arth, R. E. Beyler, andL. H. Sarett, J. Amer. chem. Soc.75, 422 (1953).

    Article  CAS  Google Scholar 

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Bloom, B.M., Agnello, E.J. & Laubach, G.D. C(14)-substituted corticosteroids. some D ring transformations in the compound S series. Experientia 12, 27–30 (1956). https://doi.org/10.1007/BF02156992

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