2520
T. Ito et al. / Tetrahedron Letters 50 (2009) 2516–2520
J.; Westphal, C. H. Nature 2007, 450, 712–716; (b) Howitz, K. T.; Bitterman, K. J.;
Cohen, H. Y.; Lamming, D. W.; Lavu, S.; Wood, J. G.; Zipkin, R. E.; Chung, P.;
Kisielewski, A.; Zhang, L. L.; Scherer, B.; Sinclair, D. A. Nature 2003, 425, 191–
196; (c) Jang, M.; Cai, L.; Udeani, G. O.; Slowing, K. V.; Thomas, C. F.; Beecher, C.
W.; Fong, H. H.; Farnsworth, N. R.; Kinghorn, A. D.; Mehta, R. G.; Moon, R. C.;
Pezzuto, J. M. Science 1997, 275, 218–220.
onstrates additional diversity of resveratrol oligomers in Diptero-
carpaceaeous plants.
Acknowledgments
6. (a) Snyder, S. A.; Zografos, A. L.; Lin, Y. Angew. Chem., Int. Ed. 2007, 46, 8186–
8191; (b) Hui, M. G.; Chen, X.; Xiao, T. W.; Bo, H.; Ren, X. T. Eur. J. Org. Chem.
2006, 5551–5554; (c) Seo, E.-K.; Chai, H.; Constant, H. L.; Santisuk, T.;
Reutrakul, V.; Beecher, C. W. W.; Farnsworth, N. R.; Cordell, G. A.; Pezzuto, J.
M.; Kinghorn, A. D. J. Org. Chem. 1999, 64, 6976–6983.
7. An acetone extract (60 g) of the dried and ground bark (1.2 kg) was subjected to
column chromatography on silica gel (EtOAcꢀCHCl3ꢀMeOHꢀH2O gradient
system) to give 57 fractions. Further purification of a combined fraction of the
42ndꢀ45th fractions (EtOAc–CHCl3–MeOH–H2O (60:30:11:2)) by vacuum
liquid chromatography (EtOAc–CHCl3–MeOH–H2O gradient system),
Sephadex LH-20 column chromatography (eluted with MeOH), and ODS
column chromatography (eluted with 40% MeOH), followed by HPLC
separation (Shiseido CAPCELL PAK C18 UG120; eluted with 43% MeOH)
isolated four compounds: 1 (320 mg), 2 (122 mg), 3 (148 mg), and 4 (82 mg).
8. Lemiere, G.; Gao, M.; De Groot, A.; Dommisse, R.; Lepoivre, J.; Pieters, L.; Buss,
V. J. Chem. Soc., Perkin Trans. 1 1995, 1775–1779.
We are grateful to Dr. S. Riswan, Herbarium Bogoriense, Indone-
sian Institute of Sciences, for collection and identification of plant
material. CD spectra of 1, 2, and (ꢀ)-
e-viniferin were recorded at
Osaka University of Pharmaceutical Sciences, and we acknowledge
the help of Professor K. Baba and Associate Professor M. Taniguchi.
We also thank the Division of Instrumental Analysis, Life Research
Center, Gifu University, for measurements of CD spectra of 3–8.
Supplementary data
Supplementary data associated with this article can be found, in
9. A mixture of water (1 ml), dioxane (3 ml), 3 (21 mg: 0.02 mmol), and osmium
tetroxide (2.0 mg) was stirred for 5 min and maintained at 24–26 °C. During
this process, sodium metaperiodate (10.7 mg, 0.05 mmol) was added over a
period of 30 min. The tan colored slurry was then stirred for additional 1.5 h to
give degradation products 5 (1.6 mg, a brown solid; ½a D25
ꢀ41.0 (c 0.1, MeOH))
ꢁ
References and notes
and 6 (4.5 mg, a pale yellow solid; ½a D25
ꢀ68.4 (c 0.1, MeOH)), respectively. A
ꢁ
similar reaction repeated with 4 (21 mg: 0.02 mmol) produced 5 (2.2 mg, a
1. (a) Ito, T.; Abe, N.; Oyama, M.; Iinuma, M. Helv. Chim. Acta 2008, 91, 1989–
1998; (b) Ito, T.; Furusawa, M.; Iliya, I.; Tanaka, T.; Nakaya, K. I.; Sawa, R.;
Kubota, Y.; Takahashi, Y.; Riswan, S.; Iinuma, M. Tetrahedron Lett. 2005, 46,
3111–3114; (c) Ito, T.; Tanaka, T.; Iinuma, M.; Iliya, I.; Nakaya, K.; Ali, Z.;
Takahashi, Y.; Sawa, R.; Shirataki, Y.; Murata, J.; Darnaedi, D. Tetrahedron
2003, 59, 5347–5363; (d) Ito, T.; Tanaka, T.; Iinuma, M.; Nakaya, K.;
Takahashi, Y.; Sawa, R.; Naganawa, H.; Chelladurai, V. Tetrahedron 2003, 59,
1255–1264; (e) Ito, T.; Tanaka, T.; Ido, Y.; Nakaya, K.; Iinuma, M.; Riswan, S.
Chem. Pharm. Bull. 2000, 48, 1959–1963.
brown solid; ½a 2D5
ꢁ
ꢀ36.8 (c 0.1, MeOH)) and 7 (6.4 mg, a pale yellow solid; ½a D25
ꢁ
+66.0 (c 0.1, MeOH)). A same treatment of (ꢀ)-
e-viniferin (454 mg: 0.1 mmol)
resulted in the isolation of degradation products 8 (160 mg, a pale yellow solid;
ꢀ142 (c 0.1, MeOH)) and 4-hydroxybenzaldehyde (49 mg).
10. All degradation products were characterized by their specific rotation,9 CD, 1
NMR (d in ppm, acetone-d6, 400 MHz) (Table S1), and FABMS spectral data.
Compound 5: CD (c 38.0 M, MeOH) nm (
): 238 (ꢀ17.4); Positive ion FABMS
½ ꢁ
a 2D5
H
l
De
m/z: 527 [M+H]+. Compound 6: CD nm (c 39.2
lM, MeOH) (De): 234 (ꢀ21.5),
272 (ꢀ6.4), 302 (+3.5); Positive ion FABMS m/z: 511 [M+H]+. Compound 7: CD
2. Kurihara, H.; Kawabata, J.; Ichikawa, S.; Mizutani, J. Agric. Biol. Chem. 1990, 54,
1097–1099.
(c 39.2 lM, MeOH) nm (De): 233 (+13.8), 272 (+5.0), 302 (ꢀ3.8); Positive ion
FABMS m/z: 511 [M+H]+. Compound 8: CD (c 27.5
(ꢀ46.5); Positive ion FABMS m/z: 365 [M+H]+.
lM, MeOH) nm (De): 237
3. Sotheeswaran, S.; Pasupathy, V. Phytochemistry 1993, 32, 1083–1092.
4. He, S.; Wu, B.; Pan, Y.; Jiang, L. J. Org. Chem. 2008, 73, 5233–5241.
5. (a) Milne, J. C.; Lambert, P. D.; Schenk, S.; Carney, D. P.; Smith, J. J.; Gagne, D. J.;
Jin, L.; Boss, O.; Perni, R. B.; Vu, C. B.; Bemis, J. E.; Xie, R.; Disch, J. S.; Ng, P. Y.;
Nunes, J. J.; Lynch, A. V.; Yang, H.; Galonek, H.; Israelian, K.; Choy, W.; Iffland,
A.; Lavu, S.; Medvedik, O.; Sinclair, D. A.; Olefsky, J. M.; Jirousek, M. R.; Elliott, P.
11. Takaya, Y.; Yan, K. X.; Terashima, K.; He, Y. H.; Niwa, M. Tetrahedron 2002, 58,
9265–9271.
12. Aminah, N. S.; Achmad, S. A.; Aimi, N.; Ghisalberti, E. L.; Hakim, E. H.; Kitajima,
M.; Syah, Y. M.; Takayama, H. Fitoterapia 2002, 73, 501–507.