A Convenient Procedure for the Synthesis of 3β-Hydroxy-6-oxo-5α-steroids. Application to the Synthesis of Laxogenin
Keywords:
Laxogenin, diastereoselective epoxidation, 3β-hydroxy-6-oxo-5α-steroidsAbstract
Abstract. convenient pathway to obtain 3β-hydroxy-6-oxo-5α-steroids from 3β-acetoxy Δ5-steroids is reported; the methodology was applied to the synthesis of laxogenin (7), substance that behaves as a plant growth hormone. This is an alternative way to produce an important functionality found in many examples of naturally occurring steroids. The developed procedure uses inexpensive reagents and can be carried out in four steps. The oxidizing and acidic steps used in this methodology did not affect the labile spiroketal side chain present in diosgenin (16).
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References
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10. Syamala, M. S.; Das, J.; Baskaran, S.; Chandrasekaran, S.; J. Org. Chem. 1992, 57, 1928; Parish, E. J.; Li, H.; Li, S.; Synth. Commun. 1995, 25, 927; Hanson, J. R.; Hitchock, P. B.; Liman, M. D.; Nagaratnam, S.; Manickavasagar, R.; J. Chem. Res. (S) 1995, 220; Parish, E. J.; Li, S.; J. Chem. Res. (S) 1996, 288; Parish, E. J.; Li, S.; J. Org. Chem. 1996, 61, 5665; Salvador, J. A. R.; Sáe Melo, M. L.; Campos Neves, A. S.; Tetrahedron Lett. 1996, 37, 687; Salvador, J. A. R.; Hanson, J. R.; J. Chem. Res. (S) 2002, 576. The authors became aware that, after submission of the present paper, a different and convenient method for β-epoxidation of Δ5-steroids using Co(II) salts and molecular oxygen had been published: Silvestre, S. M.; Salvador, J. A. R.; Clark, J. H.; J. Mol. Catal. A: Chemical 2004, 219, 143.
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2. Adam, G.; Marquardt, V.; Phytochemistry 1986, 25, 1787.
3. Jizba, J.; Herout, V.; Collect. Czech. Chem. Commun. 1967, 32, 2867.
4. Takeda, K.; Shimaoka, A.; Iwasaki, M.; Minato, H.; Chem. Pharm. Bull. 1965, 13, 691.
5. Behr, D.; Berg, J. E.; Karlsson, B.; Leander, K.; Pilotti, A. M.; Wiehager, A. C.; Acta Chem. Scand. (B) 1975, 29, 401.
6. Nakahatov, I.; Nabiev, A.; Shakirov, R.; Yusonov, S.; Khim. Prir. Soedin 1983, 6, 747. (CA 100: 188749)
7. Nakahatov, I.; Nabiev, A.; Shakirov, R.; Khim. Prir. Soedin. 1981, 4, 616. (CA 96: 65672x)
8. Okanishi, T.; Akahor, A.; Yasuda, F.; Chem. Pharm. Bull. 1965, 13, 545; Iglesias-Arteaga, M. A.; Perez Gil R.; Perez Martinez C. S.; Coll Manchado, F.; J. Chem. Soc., Perkin Trans. 1 2001, 261.
9. Henbest, H. B.; Wrigley, T. I.; J. Chem. Soc. 1957, 4765; Ramírez, J. A.; Gros, E. G.; Galagovsky, L. R.; Tetrahedron 2000, 56, 6171.
10. Syamala, M. S.; Das, J.; Baskaran, S.; Chandrasekaran, S.; J. Org. Chem. 1992, 57, 1928; Parish, E. J.; Li, H.; Li, S.; Synth. Commun. 1995, 25, 927; Hanson, J. R.; Hitchock, P. B.; Liman, M. D.; Nagaratnam, S.; Manickavasagar, R.; J. Chem. Res. (S) 1995, 220; Parish, E. J.; Li, S.; J. Chem. Res. (S) 1996, 288; Parish, E. J.; Li, S.; J. Org. Chem. 1996, 61, 5665; Salvador, J. A. R.; Sáe Melo, M. L.; Campos Neves, A. S.; Tetrahedron Lett. 1996, 37, 687; Salvador, J. A. R.; Hanson, J. R.; J. Chem. Res. (S) 2002, 576. The authors became aware that, after submission of the present paper, a different and convenient method for β-epoxidation of Δ5-steroids using Co(II) salts and molecular oxygen had been published: Silvestre, S. M.; Salvador, J. A. R.; Clark, J. H.; J. Mol. Catal. A: Chemical 2004, 219, 143.
11. Chakravorty, P. N.; Levin, R.; J. Am. Chem. Soc. 1942, 64, 2317.
12. James, D. R.; Shoope. C. W.; J. Chem. Soc. 1954, 4224.
13. Heilbron, I. M.; Jones, E. H. R.; Spring, F. S.; J. Chem. Soc. 1937, 801.
14. Fonken, G. J.; Miles, H. M.; J. Org. Chem. 1963, 28, 2432.
15. Dodson, R. G.; Riegel, B.; J. Org. Chem. 1948, 13, 424.
16. Bowers, A.; Denot, E.; Cuéllar Ibáñez, L.; Cabezas, M. E.; Ringold, H. J.; J. Org. Chem. 1962, 27, 1862.
17. Elks, J. In Rodd´s Chemistry of Carbon Compounds; Coffey, S., ed., Elsevier Publ. Co.: Amsterdam, 1971, ch. 18.
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2020-08-07
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