December 2001
1663
Chart 3
palladium-catalyzed isomerization.17) Finally, C25-apocarote-
nal 14a was condensed with C15-Wittig salt 17,18) which was
prepared from trienoate 9 by reduction with LiAlH4 followed
by treatment with PPh3·HBr, to give the condensed products
(quant.), which was purified by preparative HPLC to afford
Acta, 59, 1832—1849 (1976).
7) Acemoglu M., Prewo R., Bieri J. H., Eugster C. H., Helv. Chim. Acta,
67, 175—183 (1984).
8) Lopez L., Mele G., Fiandanese V., Cardellicchio C., Nacci A., Tetrahe-
dron, 50, 9097—9106 (1994).
9) These epoxides were prepared from b-ionone.
10) In this paper, two terms trans and cis are used to refer to the relation-
ship between C-5 methyl group and C-8 substituent.
11) a) Saulnier M. G., Kadow J. F., Tun M. M., Langley D. R., Vyas D. M.,
J. Am. Chem. Soc., 111, 8320—8321 (1989); b) Crisp G. T., Meyer A.
G., J. Org. Chem., 57, 6972—6975 (1992).
12) Soukup M., Widmer E., Lukácˇ T., Helv. Chim. Acta, 73, 868—873
(1990).
1
all-E capsanthin (42%). Its spectral data [IR, UV-VIS, H-
and 13C-NMR, MS, and CD (circular dichroism)] were in
good agreement with those reported.5)
Biological activities of capsanthin 1 except for the antioxi-
dant function are now extensively under investigation.
13) Betzer J.-F., Delaloge F., Muller B., Pancrazi A., Prunet J., J. Org.
Chem., 62, 7768—7780 (1997).
Acknowledgements We are indebted to Drs. U. Hengartner and K.
Bernhard, Hoffmann-La Roche Ltd., Basel, Switzerland for chemical sup-
port. We thank Mr. H. Kuroki for technical assistance.
14) Farina V., Krishnan B., J. Am. Chem. Soc., 113, 9585—9595 (1991).
15) Compound 13: 1H-NMR (CDCl3) d: 0.85, 1.22 and 1.39 (each 3H, s),
1.52 (1H, dd, Jϭ14.5, 3.5 Hz), 1.74 (1H, dd, Jϭ13.5, 4.5 Hz), 1.99
(1H, dd, Jϭ13.5, 8 Hz), 2.32 (3H, d, Jϭ1.5 Hz), 2.91 (1H, dd, Jϭ14.5,
8.5 Hz), 4.51 (1H, m), 6.21 (1H, br d, Jϭ8 Hz), 6.88 (1H, d, Jϭ15.5
Hz), 7.26 (1H, d, Jϭ15.5 Hz), 10.18 (1H, d, Jϭ8 Hz). IR (CHCl3)
cmϪ1: 3605, 3466, 1667, 1589. HR-MS m/z: 250.1560 (Calcd for
C15H22O3: 250.1568). [a]D25 Ϫ15.2° (cϭ1.12 in MeOH).
References and Notes
1) a) Tode C., Yamano Y., Ito M., J. Chem. Soc., Perkin Trans. 1, 1999,
1625—1626; b) Idem, Chem. Pharm. Bull., 48, 1833—1834 (2000).
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1337—1339; b) Idem, ibid., 1998, 2569—2581.
3) We have employed the numbering system used in carotenoids.
4) a) Matsufuji H., Nakamura H., Chino M., Takeda M., J. Agric. Food 16) Bernhard K., Kienzle F., Mayer H., Müller R. K., Helv. Chim. Acta,
Chem., 46, 3468—3472 (1998); b) Hirayama O., Nakamura K.,
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397—405 (1976).
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1377—1382 (1980).
6) Leuenberger H. G. W., Boguth W., Widmer E., Zell R., Helv. Chim.