4α-Methyl-5α,14β-ergosta-8,24(24 1)-dien-3̧-ol("triticusterol"): The first naturally occurring 14β(H)-steroid

Journal of the Chemical Society - Perkin Transactions 1

Volumn , Issue 4, 1999, Pages 497-500

  Akihisa, Toshihiro ^a   Kokke, Wilhelmus C M C ^b   Kpike, Kazuo ^c   Kimura, Yumiko ^d   Mizukami, Chiyo ^e   Sadaie, Aya ^a,e   Maruyama, Takenori ^c,d,e   Nikaido, Tamotsu ^e  

^a JAPAN SCIENCE AND TECHNOLOGY AGENCY   (Japan)

^b Cauldron Process Chemistry   (United States)

^c TOHO UNIVERSITY   (Japan)

^d NIHON UNIVERSITY   (Japan)

^e Support Center for Advanced Telecommunications Technology Research Foundation   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0002641582     PISSN: 0300922X     EISSN: None     Source Type: Journal    
DOI: 10.1039/a808508k     Document Type: Article

References (27)

1. L. J. Goad, and T. Akihisa, Analysis ofSterols, Blackie Academic, and Professional, London, 1997.
2. W. R. Nes, and M. L. McKean, Biochemistry of Steroids, and Other Isopentenoids, University Park Press, Baltimore, Maryland, 1977, ch. 9.
3. L. J. Goad, Methods Plant Biochem., 1991,7, 369.
4. In this context, cholesterol (or an analogue with a C-24-alkylated side chain) is considered to be an end-product of sterol biosynthesis. This makes coprostanols [5p(H)-sterols], formed by reduction of these A5-sterols, metabolites.
5. 1-3,6 They are products of a different biosynthetic pathway.
6. T. Akihisa, W. C. M. C. Kokke, and T. Tamura, Physiology, and Biochemistry of Sterols, ed. G. W. Patterson, and W. D. Nes, American Oil Chemist's Society, Champaign, Illinois, 1992, ch. 7.
7. T. Akihisa, T. Yokota, N. Takahashi, T. Tamura, and T. Matsumoto, Phytochemistry, 1989, 28, 1219.
8. 3) 0.71 (3H, s, 19-H5), 0.84 (3H, s, 18-Hj), and 3.1 (lH,m,3-H).
9. W. C. M. C. Kokke, W. Fenical, and C. Djerassi, Phytochemistry, 1981,20,127.
10. N. W. Withers, L. 1 Goad, and T. W. Goodwin, Phytochemistry, 1979,18, 899.
11. M. D. Greca, P. Monaco, and L. Previtera, Phytochemistry, 1989,28, 629.
12. R. F. Zürcher, Heir. Cliim. Ada, 1961,44,1380; 1963,46,2054.
13. Calculations were performed using MacroModel Ver. 6.0 with extended MM3 parameters. The conformation with minimum steric energy was obtained through a Metropolis Monte Carlo procedure. Final structures were depicted using the ChemSD program (Cambridge Scientific Computing Inc., Cambridge, MA).
14. F. Mohamadi, N. G. J. Richards, W. C. Guida, R. Liskamp, M. Lipton, C. Caufield, G. Chang, T. Hendrickson, and W. C. Still, J. Comput. Client., 1990, 11,440.
15. T. Akihisa, Y. Hayashi, G. W. Patterson, N. Shimizu, and T. Tamura, Phytochemistry, 1992,31, 1759.
16. M. Anastasia, A. Fiecchhi, P. Gariboldi, and G. Galli, J. Org. Client., 1980,45,2528.
17. M. Anastasia, A. Fiecchi, and A. Scala, J. Client. Soc., Perkin Trans. A 1976,378.
18. M. Anastasia, A. Scala, and G. Galli, J. Org. Client., 1976, 41, 1064.
19. M. Anastasia, G. Galli, and P. Allevi, / Org. Cliem., 1979, 44, 4983.
20. M. Anastasia, P. Allevi, P. Ciuffreda, A. Fiecchi, and A. Scala, Steroids, 1987,49,543.
21. D. G. Patterson, and C. Djerassi, J. Org. Client., 1979,44, 1866.
22. The 4a-methylsterol fraction of the oil was reported to contain gramisterol, and citrostadienol as the major components.1-2''24
23. A. Kornfeldt, and L.-B. Croon, Lipids, 1981,16, 306.
24. T. Tamura, T. Itoh, and T. Matsumoto, J. Jpn. Oil Cliem. Soc., 1973, 22, 157.
25. The abundances of compounds 1, 2, and 3 in the 4a-methylsterol fraction are 2, 1, and 2%, respectively. Main components are cycloeucalenol (20%), gramisterol (12%), and citrostadienol (37%). Another minor component is obtusifoliol (3%).
26. The interconversion between the A8- sterols, 1, and 3, by isomerization through the A'Msomer (amphisterol) as an intermediate during the sterol- isolation procedure is unlikely. The A8-steroIs can afford the stable A "4)-isomers by isomerization under acidic (HC1 in CHClj) or hydrogénation (Hj/Pt in HOAc) conditions, but the reverse reaction does not operate.27 The A8(14)-sterols give only the A'Msomers on further isomerization under acidic conditions.27
27. L. F. Fieser, and M. Fieser, Steroids, Reinhold Publishing Co., New York, 1959.