Preview

Proceedings of the National Academy of Sciences of Belarus, Chemical Series

Advanced search

Direct transformation of i-steroid methyl ethers in 6-ketones: the use in the synthesis of brassinosteroids

https://doi.org/10.29235/1561-8331-2019-55-2-175-181

Abstract

A one-step method for the transformation of 3α,5-cyclo-6β-methyl ethers of steroids into the corresponding 3α,5-cyclo-6-ketones under the action of methyl (trifluoromethyl) dioxirane has been developed. The possibilities of the method have been demonstrated by preparing 3-dehydrotesterone, the biosynthetic precursor of brassinolide.

About the Authors

A. L. Gurskii
Institute of Bioorganic Chemistry of the National Academy of Sciences of Belarus
Belarus

Alaksei L. Gurskii – Ph. D. (Chemistry), Leading researcher

5/2, Kuprevich Str., 220141, Minsk



V. N. Zhabinskii
Institute of Bioorganic Chemistry of the National Academy of Sciences of Belarus
Belarus

Vladimir N. Zhabinskii – Corresponding Member, D. Sc. (Chemistry), Associate Professor, Chief researcher

5/2, Kuprevich Str., 220141, Minsk



V. A. Khripach
Institute of Bioorganic Chemistry of the National Academy of Sciences of Belarus
Belarus

Vladimir A. Khripach – Academician, D. Sc. (Chemistry), Professor, Head of the Laboratory

5/2, Kuprevich Str., 220141, Minsk



References

1. Khripach V. A., Zhabinskii V. N., de Groot A. Brassinosteroids. A New Class of Plant Hormones. San Diego, Academic Press, 1999. 456 p. https://doi.org/10.1016/B978-0-12-406360-0.X5000-X

2. Khripach V. A., Zhabinskii V. N., Konstantinova O. V., Antonchick A. P., Schneider B. Synthesis of [26–2H3] brassinosteroids. Steroids, 2002, vol. 67, no 7, pp. 587–595. https://doi.org/10.1016/S0039-128X(02)00004-1

3. Litvinovskaya R. P., Raiman M. E., Khripach V. A. Synthesis of 28-homobrassinosteroids modifed in the 26-position. Chemistry of Natural Compounds, 2009, vol. 45, no 5, pp. 647–652. https://doi.org/10.1007/s10600-009-9439-2

4. Khripach V. A., Zhabinskii V. N., Gulyakevich O. V., Ermolovich Y. V., Konstantinova O. V. Synthesis of deuteriumlabeled (24R)-methyl brassinosteroids. Journal of Labelled Compounds & Radiopharmaceuticals, 2011, vol. 54, pp. 332–336. https://doi.org/10.1002/jlcr.1874

5. Khripach V. A., Zhabinskii V. N., Pavlovskii N. D. Synthesis of (22R,23R,24S)-24-methyl-5α-cholestane-3β,6α,22,23-tetraol, a biosynthetic precursor of brassinolide. Russian Journal of Organic Chemistry, 2001, vol. 37, no 11, pp. 1570–1574. https://doi.org/10.1023/A:1013804119279

6. Hurski A., Zhabinskii V., Khripach V. A short convergent synthesis of the side chains of brassinolide, cathasterone, and cryptolide. Tetrahedron Letters, 2013, vol. 54, no 6, pp. 584–586. https://doi.org/10.1016/j.tetlet.2012.11.094

7. Abe H., Honjo C., Kyokawa Y., Asakawa S., Natsume M., Narushima M. 3-Oxoteasterone and the epimerization of teasterone – identifcation in lily anthers and Distylium racemosum leaves and its biotransformation into typhasterol. Bioscience, Biotechnology, and Biochemistry, 1994, vol. 58, no 5, pp. 986–989. https://doi.org/10.1271/bbb.58.986

8. Angyal S. J., James K. Oxidative demethylation with chromium trioxide in acetic acid. Carbohydrate Research, 1970, vol. 12, no 1, pp. 147–149. https://doi.org/10.1016/S0008-6215(00)80237-2

9. Amati A., Dosualdo G., Zhao L., Bravo A., Fontana F., Minisci F., Bjørsvik H.-R. Catalytic processes of oxidation by hydrogen peroxide in the presence of Br2 or HBr. Organic Process Research & Development, 1998, vol. 2, no 4, pp. 261–269. https://doi.org/10.1021/op980028j

10. Suzuki H., Takeuchi T., Mori T. Direct oxidation of methyl ethers to carbonyl compounds with a combination of nitrogen dioxide and water in the presence or absence of ozone. Bulletin of the Chemical Society of Japan, 1997, vol. 70, no 12, pp. 3111–3115. https://doi.org/10.1246/bcsj.70.3111

11. Olah G. A., Welch J., Ho T.-L. Synthetic methods and reactions. 17. Uranium hexafluoride, a convenient new oxidizing agent for organic synthesis. Journal of the American Chemical Society, 1976, vol. 98, no 21, pp. 6717–6718. https://doi.org/10.1021/ja00437a059

12. Zhang C., Srivastava P., Ellis-Guardiola K., Lewis J. C. Manganese terpyridine artifcial metalloenzymes for benzylic oxygenation and olefn epoxidation. Tetrahedron, 2014, vol. 70, no 27, pp. 4245–4249. https://doi.org/10.1016/j.tet.2014.03.008

13. Olah G. A., Gupta B. G., Fung A. P. Cerium(IV) ammonium nitrate-catalyzed oxidative cleavage of alkyl and silyl ethers with sodium bromate. Synthesis, 1980, no 11, pp. 897–898. https://doi.org/10.1055/s-1980-29258

14. Gilissen P. J., Blanco-Ania D., Rutjes F. P. J. T. Oxidation of secondary methyl ethers to ketones. The Journal of Organic Chemistry, 2017, vol. 82, no 13, pp. 6671–6679. https://doi.org/10.1021/acs.joc.7b00632

15. van Heerden F. R., Dixon J. T., Holzapfel C. W. Direct transformation of steroidal ethers into ketones by dimethyldioxirane. Tetrahedron Letters, 1992, vol. 33, no 48, pp. 7399–7402. https://doi.org/10.1016/S0040-4039(00)60199-5

16. Hurski A. L., Zhabinskii V. N., Khripach V. A. A new approach to the side chain formation of 24-alkyl-22-hydroxy steroids: application to the preparation of early brassinolide biosynthetic precursors. Steroids, 2012, vol. 77, no 7, pp. 780–790. https://doi.org/10.1016/j.steroids.2012.03.010

17. Aburatani M., Takeuchi T., Mori K. Facile syntheses of brassinosteroids: brassinolide, castasterone, teasterone and typhasterol. Agricultural and Biological Chemistry, 1987, vol. 51, no 7, pp. 1909–1913. https://doi.org/10.1271/bbb1961.51.1909

18. Khripach V. A., Zhabinskii V. N., Gulyakevich O. V., Konstantinova O. V., Misharin A. Y., Mekhtiev A. R., Timofeev V. P., Tkachev Y. V. Synthesis of secasterol and 24-episecasterol and their toxicity for MCF-7 cells. Russian Journal of Bioorganic Chemistry, 2010, vol. 36, no 6, pp. 746–754. https://doi.org/10.1134/S1068162010060117

19. Yokota T., Nakayama M., Wakisaka T., Schmidt J., Adam G. 3-Dehydroteasterone, a 3,6-diketobrassinosteroid as a possible biosynthetic intermediate of brassinolide from wheat grain. Bioscience, Biotechnology, and Biochemistry, 1994, vol. 58, no 6, pp. 1183–1185. https://doi.org/10.1271/bbb.58.1183

20. Suzuki H., Inoue T., Fujioka S., Takatsuto S., Yanagisawa T., Yokota T., Murofushi N., Sakurai A. Possible involvement of 3-dehydroteasterone in the conversion of teasterone to typhasterol in cultured cells of Catharanthus roseus. Bioscience, Biotechnology, and Biochemistry, 1994, vol. 58, no 6, pp. 1186–1188. https://doi.org/10.1271/bbb.58.1186


Review

Views: 729


Creative Commons License
This work is licensed under a Creative Commons Attribution 4.0 License.


ISSN 1561-8331 (Print)
ISSN 2524-2342 (Online)