Synthesis and biological activity of 6a-carbabrassinolide: B-ring homologation of 6-oxo-steroid to 6-oxo-7a-homosteroid with trimethylsilyldiazomethane-boron trifluoride etherate

Tetrahedron Letters

Volumn 40, Issue 12, 1999, Pages 2359-2362

  Seto, Hideharu ^a   Fujioka, Shozo ^a   Koshino, Hiroyuki ^a   Hayasaka, Hideki ^a   Shimizu, Takeshi ^a   Yoshida, Shigeo ^a   Watanabe, Tsuyoshi ^a,b  

^a INST OF PHYS AND CHEMICAL RESEARCH   (Japan)

^b Tama Biochemical Co Ltd   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ETHER DERIVATIVE; HOMOSTEROID; KETONE; OXOSTEROID; PHYTOHORMONE; STEROID; TRIMETHYLSILYL DERIVATIVE;

ARTICLE; BIOASSAY; CHEMICAL MODIFICATION; CHEMICAL STRUCTURE; DRUG ACTIVITY; STEREOCHEMISTRY; STEROIDOGENESIS;

EID: 0033583268     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(99)00186-0     Document Type: Article

References (22)

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2. 2. Marquardt, V.; Adam, G. in Chemistry of Plant Protection Ebing, W. Ed.-in-Chief; Springer-Verlag: New York, 1991; vol. 7, pp. 103-139; Seto, H.; Fujioka, S.; Koshino, H.; Suenaga, T.; Yoshida, S.; Watanabe, T.; Takatsuto, S. J. Chem. Soc., Perkin Trans. 1 1998, 3355-3358; and references cited therein.
3. 2. Marquardt, V.; Adam, G. in Chemistry of Plant Protection Ebing, W. Ed.-in-Chief; Springer-Verlag: NewYork, 1991; vol. 7, pp. 103-139; Seto, H.; Fujioka, S.; Koshino, H.; Suenaga, T.; Yoshida, S.; Watanabe, T.; Takatsuto, S. J. Chem. Soc., Perkin Trans. 1 1998, 3355-3358; and references cited therein.
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6. 3. Okada, K.; Mori, K. Agric. Biol. Chem. 1983, 47, 89-95; Kishi, T.; Wada, K.; Ciuffreda, P.; Fiecchi, A.; Scala, A. J. Org. Chem. 1985, 50, 321-325; Anastasia, M.; Allevi, P.; Ciuffreda, P.; Fiecchi, A.; Scala, A. J. Chem. Soc., Perkin Trans. 1 1986, 2117-2121; Anastasia, M.; Allevi, P.; Marumo, S.; Mori, K. Agric. Biol. Chem. 1986, 50, 1821-1830.
7. 3. Okada, K.; Mori, K. Agric. Biol. Chem. 1983, 47, 89-95; Kishi, T.; Wada, K.; Ciuffreda, P.; Fiecchi, A.; Scala, A. J. Org. Chem. 1985, 50, 321-325; Anastasia, M.; Allevi, P.; Ciuffreda, P.; Fiecchi, A.;Scala, A. J. Chem. Soc., Perkin Trans. 1 1986, 2117-2121; Anastasia, M.; Allevi, P.; Marumo, S.; Mori, K. Agric. Biol. Chem. 1986, 50, 1821-1830.
8. 4. During the course of our work, a preceding paper on some novel brassinolide analogs including 2 appeared: Back, T. G; Baron, D. L.; Luo, W.; Nakajima, S. K.; Janzen, L.; Pharis, R. P. Proceedings of the 24th Annual Meeting of the Plant Growth Regulation Society of America, Atlanta, GA, 1997, pp. 107-110. However, the synthetic method and detailed biological activity of 2 can not be found out therein.
9. 5. Fujioka, S.; Noguchi, T.; Takatsuto, S.; Yoshida, Y. Phytochemistry 1998, 49, 1841-1847.
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13. (b) Maruoka, K.; Concepcion, A. B.; Yamamoto, H. Synthesis 1994, 1283-1290; Mori, Y.; Yaegashi, K.; Furukawa, H. J. Am. Chem. Soc.1997, 119, 4557-4558; Yang, S.; Hungerhoff, B.; Metz, P. Tetrahedron Lett. 1998, 39, 2097-2098.
14. (b) Maruoka, K.; Concepcion, A. B.;Yamamoto, H. Synthesis 1994, 1283-1290; Mori, Y.; Yaegashi, K.; Furukawa, H. J. Am. Chem. Soc. 1997, 119, 4557-4558; Yang, S.; Hungerhoff, B.; Metz, P. Tetrahedron Lett. 1998, 39, 2097-2098.
15. (b) Maruoka, K.; Concepcion, A. B.;Yamamoto, H. Synthesis 1994, 1283-1290; Mori, Y.; Yaegashi, K.; Furukawa, H. J. Am. Chem. Soc.1997, 119, 4557-4558; Yang, S.; Hungerhoff, B.; Metz, P. Tetrahedron Lett. 1998, 39, 2097-2098.
16. 2, 5% palladium on charcoal, AcOEt, rt, 1 atom, 2 h, 98%, mp 109 °C].
17. 3), 11.82 (C-18), 12.21 (C-29), 15.83 (C-19), 19.01 (C-21), 19.24 and 20.03 (C-26 and C-27), 22.76 (C-2), 22.94 (C-11), 23.53 (C-28), 25.40 (C-4), 25.76 (C-3), 25.95 (C-15), 26.54 (C-23), 28.08 (C-16), 29.59 (C-25), 30.43 (C-7a), 34.31 (C-22), 36.58 (C-20), 38.63 (C-10), 40.29 (C-12), 41.61 (C-8), 41.72 (C-1), 42.27 (C-13), 46.29 (C-24), 50.67 (C-7), 54.77 (C-5), 56.34 (C-14), 56.63 (C-17), 59.64 (C-9), 212.79 (C-6).
18. 10. The sterically disadvantageous axial attack of carbanions to cyclohexanones like this is well documented in organoaluminum Lewis acid-promoted alkylation, see Maruoka, K.; Itoh, T.; Sakurai, M.; Nonoshita, K.; Yamamoto, H. J. Am. Chem. Soc. 1988, 110, 3588-3597.
19. 11. For the stereoelectronic requirements for the Tiffeneau-Demjanov type rearrangements, see ref. 6 and Deslongchamps, P. Stereoelectronic Effects in Organic Chemistry, Pergamon Press, Oxford, 1983; pp. 163-208; and references cited therein.
20. 12. Takatsuto, S.; Yazawa, N.; Ishiguro, M.; Morisaki, M.; Ikekawa, N. J. Chem. Soc., Perkin Trans. 1 1984, 139-146.
21. 13. Watanabe, T.; Kuriyama, H.; Furuse, T.; Kobayashi, K.; Takatsuto, S. Agric. Biol. Chem. 1988, 52, 2117-2118.
22. 2O).