780
D. Rosas-Ramírez et al. / Phytochemistry 72 (2011) 773–780
(1H, dd, J = 9.5, 6.0 Hz, Rha0-5), 4.53 (1H, dd, J = 9.5, 3.5 Hz, Rha0-3),
6.19 (1H, bs, Rha0-1), 4.39 (1H, dd, J = 9.5, 9.5 Hz, Rha0-4), 4.77 (1H,
bs, Rha0-2), 1.57 (3H, d, J = 6.0 Hz, Rha00-6), 4.32 (1H, dd, J = 9.0,
5.5 Hz, Rha00-5), 4.23 (1H, dd, J = 9.0, 9.0 Hz, Rha00-4), 4.44 (1H, dd,
J = 9.0, 3.0 Hz, Rha00-3), 6.27 (1H, bs, Rha00-1), 4.80 (1H, bs, Rha00-
2), 0.89 (3H, t, J = 7.0 Hz, Jal-16), 2.62 (2H, t, J = 7.3 Hz, CH2CO2),
3.88 (1H, bs, Jal-11); 13C NMR (C5D5N, 125 MHz) d 17.1 (CH3,
Fuc-6), 76.6 (CH, Fuc-3), 71.1 (CH, Fuc-5), 73.4 (CH, Fuc-4), 75.4
(CH, Fuc-2), 101.6 (CH, Fuc-1), 19.0 (CH3, Rha-6), 67.1 (CH, Rha-
5), 72.7 (CH, Rha-2), 73.2 (CH, Rha-3), 80.6 (CH, Rha-4), 101.4
(CH, Rha-1), 18.8 (CH3, Rha0-6), 73.0 (CH, Rha0-2), 79.5 (CH, Rha0-
4), 73.4 (CH, Rha0-3), 68.3 (CH, Rha0-5), 102.8 (CH, Rha0-1), 18.4
(CH3, Rha00-6), 70.2 (CH, Rha00-5), 72.8 (CH, Rha00-3), 73.9 (CH,
Rha00-4), 72.3 (CH, Rha00-2), 103.0 (CH, Rha00-1), 14.3 (CH3, Jal-16),
35.7 (CH2CO2), 77.9 (CH, Jal-11), 172.6 (C, Jal-1).
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Operculinic acid C (5 mg) in 4 N HCl (5 mL) was heated at 90 °C
for 2 h. The reaction mixture was diluted with H2O (2.5 mL) and
extracted with Et2O (15 mL). The aqueous phase was neutralized
with 1 N KOH, extracted with n-BuOH (20 mL), and concentrated
to give a colorless solid. The residue was analyzed by HPLC: Waters
standard column for carbohydrate analysis (3.9 ꢁ 300 mm, 10
using an isocratic elution of CH3CN–H2O (17:3), a flow rate of 1 mL/
min, and a sample injection of 20 L (sample concentration: 2 mg/
lm),
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1034.
l
mL). Co-elution experiments with standard carbohydrate samples
allowed the identification of rhamnose (tR = 6.9 min) and fucose
(tR = 8.3 min). Each of these eluates was individually collected, con-
centrated, and dissolved in H2O. Optical activity was recorded after
stirring the solutions for 2 h at room temperature and values were
identical with those registered for commercially available samples:
Mendoza-Espinoza, J.A., López-Vallejo, F., Fragoso-Serrano, M., Pereda-Miranda, R.,
Cerda-García-Rojas,
C.M.,
2009.
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reassignment,
absolute
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Noda, N., Horiuchi, Y., 2008. The resin glycosides from the sweet potato (Ipomoea
batatas L. Lam.). Chem. Pham. Bull. 56, 1607–1610.
Noda, N., Takahashi, N., Kawasaki, T., Miyahara, K., Hanazono, H., Yang, C.R., 1995. A
L
-rhamnose [
(c 0.1, H2O), control [
578 + 83, [ 546 + 94, [
trol [ D + 81 (c 0.1, H2O). The organic phase-soluble product was
methylated with CH2N2 to further perform its separation by HPLC
m), an iso-
a
]
598 + 8, [
a
]
a
]
578 + 8, [
D + 8 (c 0.1, H2O);
436 + 155, [ 365 + 236 (c 0.1, H2O), con-
a
]
546 + 9, [
a
D
]
436 + 15, [
a
]
365 + 21
a
-fucose [
a]598 + 79,
[
a
]
a
]
]
a]
Novel resin glycoside, merremin (tuguajalapin
X dimer), from Merremia
hungaiensis. Chem. Pharm. Bull. 43, 1061–1063.
a]
Noda, N., Takahashi, N., Miyahara, K., Yang, C.R., 1998. Stoloniferins VIII–XII, resin
glycosides from Ipomoea stolonifera. Phytochemistry 48, 837–841.
Noda, N., Yoda, S., Kawasaki, T., Miyahara, K., 1992. Resin Glycosides XV. Simonins I-
V, ether-soluble resin glycosides (jalapins) from the roots of Ipomoea batatas
(cv. Simon). Chem. Pharm. Bull. 40, 3163–3168.
Ono, M., Fujimoto, K., Kawata, M., Fukunaga, T., Kawasaki, T., Miyahara, K., 1992.
Resin Glycosides. XIII. Operculins VI, XI, XII, XIII, XIV and XV, the ether-soluble
resin glycosides (‘‘jalapin’’) from rhizoma jalapae brasiliensis (roots of Ipomoea
operculata). Chem. Pharm. Bull. 40, 1400–1403.
Ono, M., Kawasaki, T., Miyahara, K., 1989. Resin Glycosides. V. Identification and
characterization of the component organic and glycosidic acids of the ether-
soluble crude resin glycosides (‘‘jalapin’’) from rhizoma jalapae brasiliensis (roots
of Ipomoea operculata). Chem. Pharm. Bull. 37, 3209–3213.
Pereda-Miranda, R., Bah, M., 2003. Biodynamic constituents in the Mexican morning
Glories: purgative remedies transcending boundaries. Curr. Top. Med. Chem. 3,
111–131.
using a normal phase ISCO column (10 ꢁ 250 mm, 10
l
cratic elution of hexane–CHCl3-Me2CO (6:3:1), and a flow rate of
0.5 mL/min to afford methyl (11S)-hydroxyhexadecanoate (jala-
pinolic acid methyl ester): tR 16.4 min; mp 42–44 °C; [a]D + 7.3 (c
2, CHCl3); 13C NMR: 174.4, 72.0, 51.4, 37.5, 37.4, 34.1, 31.9, 29.6,
29.5, 29.4, 29.2, 29.1, 25.6, 25.3, 24.9, 22.6, 14.1. This aglycone
(1 mg) was derivatized with Sigma Sil-A and analyzed by GC–MS
analysis, (tR 12.8 min): m/z [M]+ 358 (0.3), 343 (0.5), 311 (10.5),
287 (59.7), 173 (100), 73 (46.3) (Pereda-Miranda et al., 2006).
Acknowledgements
Pereda-Miranda, R., Escalante-Sánchez, E., Escobedo-Martínez, C., 2005.
Characterization of lipophilic pentasaccharides from beach morning glory
(Ipomoea pes-caprae). J. Nat. Prod. 68, 226–230.
Pereda-Miranda, R., Fragoso-Serrano, M., Escalante-Sánchez, E., Hernández-Carlos,
B., Linares, E., Robert, B., 2006. Profiling of the resin glycoside content of
Mexican jalap roots with purgative activity. J. Nat. Prod. 69, 1460–1466.
Pereda-Miranda, R., Hernández-Carlos, B., 2002. HPLC Isolation and structural
elucidation of diastereomeric niloyl ester tetrasaccharides from Mexican
scammony root. Tetrahedron 58, 3145–3154.
Pereda-Miranda, R., Rosas-Ramírez, D., Castañeda-Gómez, J., 2010. Resin Glycosides
from the morning glory family. In: Kinghorn, A.D., Falk, H., Kobayashi, J. (Eds.),
Progress in the Chemistry of Organic Natural Products, vol. 92. SpringerWien,
New York, pp. 77–152.
This research was supported by Dirección General de Asuntos
del Personal Académico, UNAM (IN217310) and CONACyT
(101380-Q). D.R.-R. and E.E.-S. are grateful to CONACyT for gradu-
ate student scholarships. Thanks are due to Dr. Davinia Mills (Bio-
Centre Facility, University of Reading, UK), Georgina Duarte, and
Margarita Guzmán (Facultad de Química, UNAM) for the recording
of mass spectra. We also wish to thank Dr. Mabel Fragoso–Serrano
(Facultad de Química, UNAM) for HPLC technical assistance.
Yoshikawa, K., Yagi, C., Hama, H., Tanaka, M., Arihara, S., Hashimoto, T., 2010.
Ipomotaosides A–D, resin glycosides from the aerial parts of Ipomoea batatas
and their inhibitory activity against COX-1 and COX-2. J. Nat. Prod. 73, 1763–
1766.
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