September 2002
1289
Catalytic Hydrogenation of 2 to 4 A mixture of 2 (0.6 mg) and 10% sity of Pharmacy and Life Science for measurement of mass spectra.
palladium on charcoal (2 mg) in ethyl acetate (0.5 ml) was vigorously stirred
under a hydrogen atmosphere at room temperature for 3.5 h. The mixture References and Notes
was filtered through a short Celite column, rinsed with ethyl acetate, and the
filtrate was concentrated under reduced pressure. The residue was purified
by silica gel flash column chromatography [hexane–ethyl acetate (3 : 1)] and
HPLC [hexane–2-propanol (9 : 1)] to obtain diol 4 (0.6 mg, 100% yield) as a
1) Present address: Department of Pharmacognosy, Faculty of Pharma-
ceutical Sciences, Toyama Medical and Pharmaceutical University,
2630 Sugitani, Toyama 930–0194, Japan.
2) Iwashima M., Terada I., Okamoto K., Iguchi K., J. Org. Chem., 67,
2977—2981 (2002).
3) Watanabe K., Tsuda Y., Iwashima M., Iguchi K., J. Nat. Prod., 63,
258—260 (2000).
25
11)
Ϫ1
white solid. [a] ϩ13.3° (cϭ0.06, CHCl3). IR (dry film) nmax cm
:
D
1
3
0
406, 3311, 2926. H-NMR (400 MHz, CDCl ) d ppm: 0.62 (3H, s, H-18),
3
.78 (3H, d, Jϭ6.8 Hz, H-27), 0.79 (3H, d, Jϭ6.8 Hz, H-26), 0.83 (3H, d,
Jϭ6.9 Hz, H-28), 0.94 (3H, d, Jϭ6.5 Hz, H-21), 1.13 (3H, s, H-19), 4.12
4) Iwashima M., Nara K., Nakamichi Y., Iguchi K., Steroids, 66, 25—32
(2001).
5) Iguchi K., Shimura H., Yang Z., Yamada Y., Steroids, 58, 410—413
(1993).
6) Meyer B. N., Ferrigni N. R., Putnam J. E., Jacobsen L. B., Nichols D.
E., McLaughlin J. L., Planta Med., 45, 31—34 (1982).
7) Yamori T., Matsunaga A., Sato A., Yamazaki K., Komi A., Ishizu K.,
Mita I., Edatsugi H., Matsuba Y., Takezawa K., Nakanishi O., Kohno
H., Nakajima Y., Komatsu H., Andoh T., Tsuruo T., Cancer Res., 59,
4042—4049 (1999).
1
3
(
1H, tt, Jϭ5.2, 10.6 Hz, H-3). C-NMR (100 MHz, CDCl ) d ppm: 11.0,
3
1
3
1
5.5, 17.6, 18.9, 20.5, 23.1, 23.3, 23.4, 23.5, 28.7, 29.5, 29.7, 30.7, 31.0,
1.5, 33.7, 36.7, 36.7, 39.1, 40.8, 41.9, 42.1, 51.6, 54.6, 67.2, 74.3, 129.5,
32.8. HR-EI-MS m/z: 398.3534 (Calcd for C H O: 398.3549 [MϪ
2
8
46
ϩ
H O] ).
2
Preparation of 4 from Ergosterol The oxidation reaction was carried
5
,12)
out according to the procedure described in the literature.
of products was separated by silica gel flash column chromatography
hexane–ethyl acetate (4 : 1)], followed by MPLC separation [reverse phase,
MeOH–H O (9 : 1)] to afford 9(11)-dehydro-5a,8a-epidioxyergosterol (5,
The mixture
[
8) Gulavita N. K., de Siva E. D., Hagadone M. R., Karuso P., Scheuer P.
J., J. Org. Chem., 51, 5136—5139 (1986).
2
2
5 mg, 12% yield) as a faint yellow solid. A mixture of 5 (4.9 mg) and 10%
palladium on charcoal (5 mg) in ethyl acetate (3 ml) was vigorously stirred
under a hydrogen atmosphere at room temperature for 3 h. The mixture was
9) Kassuhlka K. E., Potts B. C. M., Faulkner D. J., J. Org. Chem., 56,
3747—3750 (1991) and references cited therein.
filtered through a short Celite column, and the filtrate was concentrated 10) Sullivan B. W., Faulkner D. J., Okamoto K. T., Chen M. H. M., Clardy
under reduced pressure. The residue was purified by silica gel flash column J., J. Org. Chem., 51, 5134—5136 (1986).
chromatography [hexane–ethyl acetate (1 : 1)], followed by HPLC separation 11) Hallsworth A. S., Henbest H. B., Wrigley T. I., J. Chem. Soc., 1957,
[
normal phase, hexane–2-propanol (9 : 1)] to obtain diol 4 (2.8 mg, 59%
1969—1981 (1957). This paper described the optical rotation of 4 as
[a]D ϩ34° without any information about either the concentration or
the solvent.
25
yield) as a white solid. [a] ϩ10.6° (cϭ0.11, CHCl ). The spectral data of
4
D
3
prepared by this method were identical to those of 4 from natural 2.
1
2) Windaus A., Brunken J., Ann. Chem., 460, 225—235 (1928).
Acknowledgments The authors thank Dr. Y. Shida at the Tokyo Univer-