November 2005
1421
brine, then dried over MgSO powder and filtered. Removal of the solvent 14) Morikawa T., Tao J., Ando S., Matsuda H., Yoshikawa M., J. Nat.
4
from the filtrate under reduced pressure furnished a residue, which was sepa-
Prod., 66, 638—645 (2003).
rated by HPLC [MeOH–H O (70 : 30, v/v)] to give 1b (0.7 mg, 53%) or 2b
15) Tao J., Morikawa T., Toguchida I., Ando S., Matsuda H., Yoshikawa
M., Bioorg. Med. Chem., 10, 4005—4012 (2002).
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2
(
(
0.7 mg, 51%), respectively. Using a similar procedure, (S)-MTPA esters [1c
1.0 mg, 53%) or 2c (1.2 mg, 51%)] were obtained from 1a or 2a (1.0 mg
each), respectively, using (S)-MTPA (4.9 mg), EDC·HCl (4.2 mg), and 4-
DMAP (1.6 mg).
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1
1
b: H-NMR (500 MHz, CDCl ) δ: 1.06, 1.16, 1.26, 2.27 (each 3H, all s,
3
1
1
2, 13, 11, 10-H ), [1.44 (1H, dd, Jꢀ3.4, 12.5 Hz), 1.91 (1H, dd, Jꢀ12.5,
3
2.5 Hz), 2-H ], 3.54 (3H, s, –OCH ), 4.11 (1H, d, Jꢀ3.4 Hz, 4-H), 5.28
2
3
(
1H, ddd, Jꢀ3.4, 3.4, 12.5 Hz, 3-H), 6.27, 6.96 (1H each, both d, Jꢀ16.5 Hz, 19) Nawwar M. A. M., Hussein S. A. M., Merfort I., Phytochemistry, 37,
8
, 7-H), [7.40—7.42 (3H, m), 7.48—7.50 (2H, m), Ph-H].
1175—1177 (1994).
1
1
c: H-NMR (500 MHz, CDCl ) δ: 1.06, 1.15, 1.30, 2.29 (each 3H, all s, 20) Wang M., Simon J. E., Aviles I. F., He K., Zheng Q. Y., Tadmor Y., J.
3
1
1
2, 13, 11, 10-H ), [1.44 (1H, dd, Jꢀ3.4, 12.5 Hz), 1.83 (1H, dd, Jꢀ12.5,
2.5 Hz), 2-H ], 3.52 (3H, s, –OCH ), 4.21 (1H, d, Jꢀ3.4 Hz, 4-H), 5.28
Agric. Food Chem., 51, 601—608 (2003).
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3
2
3
(
8
1H, ddd, Jꢀ3.4, 3.4, 12.5 Hz, 3-H), 6.29, 6.98 (1H each, both d, Jꢀ16.5 Hz, 22) Tomas F., Ferreres F., Barberan F. A. T., J. Nat. Prod., 48, 506—507
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1
2
b: H-NMR (500 MHz, pyridine-d ) δ: 1.05, 1.15, 1.99, 2.33 (each 3H, 23) Markham K. R., Ternai B., Stanley R., Geiger H., Marby T. J., Tetrahe-
5
all s, 13, 12, 11, 10-H ), [1.91 (1H, dd, Jꢀ3.4, 12.5 Hz), 2.45 (1H, dd,
dron, 34, 1389—1397 (1978).
3
Jꢀ12.5, 12.5 Hz), 2-H ], 3.74 (3H, s, –OCH ), 4.47 (1H, d, Jꢀ3.4 Hz, 4-H),
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2
3
5
.50 (1H, ddd, Jꢀ3.4, 3.4, 12.5 Hz, 3-H), 6.32, 7.35 (1H each, both d,
Jꢀ16.5 Hz, 8, 7-H), [7.42—7.47 (3H, m), 7.94 (2H, d, Jꢀ7.6 Hz), Ph-H].
1
2
c: H-NMR (500 MHz, pyridine-d ) δ: 0.96, 1.13, 2.01, 2.33 (each 3H,
5
all s, 13, 12, 11, 10-H ), [1.75 (1H, dd, Jꢀ3.4, 12.5 Hz), 2.38 (1H, dd, 26) Kobayashi H., Karasawa H., Miyase T., Fukushima S., Chem. Pharm.
3
Jꢀ12.5, 12.5 Hz), 2-H ], 3.81 (3H, s, –OCH ), 4.63 (1H, d, Jꢀ3.4 Hz, 4-H),
Bull., 33, 1452—1457 (1985).
2
3
5
.52 (1H, ddd, Jꢀ3.4, 3.4, 12.5 Hz, 3-H), 6.30, 7.32 (1H each, both d, 27) Rahman M. M. A., Dewick P. M., Jackson D. E., Lucas J. A., Phyto-
Jꢀ16.5 Hz, 8, 7-H), [7.40—7.47 (3H, m), 8.00 (2H, d, Jꢀ7.6 Hz), Ph-H].
Bioassay. Inhibitory Effect on Aldose Reductase Activity Aldose
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(1991).
52—57)
reductase activity was assayed by the method described previously.
The
supernatant fluid of rat lens homogenate was used as a crude enzyme. The
incubation mixture contained 135 mM Na, K-phosphate buffer (pH 7.0),
1
00 mM Li SO , 0.03 mM NADPH, 1 mM DL-glyceraldehyde as a substrate,
2 4
and 100 ml of enzyme fraction, with or without 25 ml of sample solution, in a
total volume of 0.5 ml. The reaction was initiated by the addition of NADPH
31) Greca M. D., Ferrara M., Fiorentino A., Monaco P., Previtera L., Phy-
tochemistry, 49, 1299—1304 (1998).
at 30 °C. After 30 min, the reaction was stopped by the addition of 150 ml of 32) Comte G., Allais D. P., Chulia A. J., Vercauteren J., Pinaud N., Phyto-
0
.5 M HCl. Then, 0.5 ml 6 M NaOH containing 10 mM imidazole was added,
chemistry, 44, 1169—1173 (1997).
and the solution was heated at 60 °C for 20 min to convert NADP to a fluo-
rescent product. Fluorescence was measured using a fluorophotometer (Lu-
33) Miyase T., Ueno A., Takizawa N., Kobayashi H., Oguchi H., Chem.
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length of 360 nm and an emission wavelength of 460 nm.
Pharm. Bull., 35, 1109—1117 (1987).
35) Kitajima J., Ishikawa T., Tanaka Y., Ono M., Ito Y., Nohara T., Chem.
Acknowledgments The authors would like to thank Dr. Seiichi Yamaji,
Assistant Professor of the Institute of Natural Medicine, Toyama Pharma-
ceutical and Medical University, Japan for identifying the plant material.
Part of this work was supported by the 21st COE program and the Academic
Frontier Project of the Ministry of Education, Culture, Sports, Science and
Technology of Japan.
Pharm. Bull., 46, 1587—1590 (1998).
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ical data with commercially obtained samples.
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1
13
9)
47) The H- and C-NMR spectra of 1, 2, 1a, and 2a were assigned with
7
the aid of distortionless enhancement by polarization transfer (DEPT),
1
1
13
1
1
1
1
1
homo- and hetero-correlation spectroscopy ( H– H, C– H COSY),
and HMBC experiments.
2
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Pharm. Bull., 51, 654—662 (2003). stereostructure was not determined. This is the first report of the struc-
8
51)