350 J ournal of Natural Products, 2002, Vol. 65, No. 3
Zou et al.
859 [M + H]+, 655 [M - Ac - glc + H]+, and 457 [M - 2glc -
Ac - 2H2O + H]+; (negative mode) m/z 857 [M - H]-, 653 [M
- glc - Ac - H]-; APIMS/MS (negative mode, parent ion m/z
857) 857 [M - H]-, 815 [M - Ac - H]-, 737 [857-120]-, 695
[M - glc - H]-, 653 [M - glc - Ac - H]-, 635 [695 - 60]-,
695 [815 - 120]-, 491 [M - 2glc - Ac - H]-; anal. C 60.27%,
H 8.68%, calcd for C44H74O16‚H2O, C 60.01%, H 8.63%.
601 [M - 2glc - rha - HOAc - H2O - H]-, 475 [M - 3glc -
rha - H]-. anal. C 56.66%, H 8.26%, calcd for C56H94O24‚2H2O,
C 56.57%, H 8.20%.
Alk a lin e Hyd r olysis of Com p ou n d s 1, 4, a n d 6. To a
solution of 1 (4.2 mg), 4 (2.9 mg), and 6 (2.2 mg) in H2O (2.0
or 1.5 mL) was added a portion (2.0 or 1.5 mL) of 50% aqueous
NH4OH, respectively. After stirring at 35 °C for 16 h, the
solution was neutralized by adding 2.0 M HCl solution and
then desalted with Amberlite MB-3. The eluate was concen-
trated under reduced pressure and subjected to preparative
HPLC (mobile phase, CH3CN-H2O, 22:78 v/v; flow rate, 8.0
mL/min) to afford 1a (tR ) 16.3 min, 2.7 mg), 11 (tR ) 19.2
min, 1.8 mg), and 5 (tR ) 25.6 min, 1.4 mg) from 1, 4, and 6,
respectively. 1a 16 was obtained as a white amorphous powder,
20
Yesa n ch in osid e B (2): white amorphous powder, [R]D
+11.3°(c 0.1, 40% CH3CN); IR (KBr) νmax 3392, 2931, 2874,
1639, 1563 cm-1; 1H NMR and 13C NMR (see Tables 1, 2, and
3); APIMS (positive mode, MeOH/NH4OAc) m/z 996 [M +
NH4]+, 979 [M + H]+; APIMS/MS (positive, parent ion m/z 996)
961 [M - H2O + H]+, 799 [M - glc - H2O + H]+, 637 [M -
2glc - H2O + H]+, 475 [M - 3glc - H2O + H]+, 457 [M - 3glc
- 2H2O + H]+, 439 [M - 3glc - 3H2O + H]+, 421 [M - 3glc -
4H2O + H]+; (negative, MeOH/NH4OAc) m/z 1037 [M + OAc]-,
977 [M - H]-, 961 [M - OH]-, 815 [M - glc - H]-, 637 [M -
2glc - OH]-; APIMS/MS (negative, parent ion m/z 977) 977
[M - H]-, 815 [M - glc - H]-, 797 [M - glc - H2O-H]-, 653
[M - 2glc - H]-, 617 [M - 2glc - 2H2O - H]-, 491 [M - 3glc
- H]-. anal. C 56.80%, H 8.48%, calcd for C48H82O20‚2H2O, C
56.56%, H 8.46%.
20
mp 173-176 °C; [R]D +1.3° (c 0.1, 40% CH3CN). The HPLC,
API-MS, IR, and 1H NMR data of 5 and 11 were in good
agreement with those of yesanchinoside E and ginsenoside
Rg1,7 respectively.
Deter m in a tion of Su ga r Com p on en ts.21,22 Compounds
1-6 (each 0.8 mg) were hydrolyzed with 10% HCl in 40% CH3-
CN solution by reflux at 80 °C for 4 h. After neutralization
with 2.0 M NaOH, the mixture was extracted with CHCl3. The
water layer was desalted with Amberlite MB-3 and evaporated
to dryness under reduced pressure. The residue was dissolved
in anhydrous pyridine (100 µL), and 200 µL of 0.1 M L-cysteine
methyl ester hydrochloride was added. The mixture was
stirred at 60 °C for 1 h, then 150 µL of HMDS-TMCS
(hexamethyldisilazane-trimethylchlorosilane-pyridine, 2:1:
10) was added, and the mixture was stirred at 60 °C for
another 30 min. After centrifugation, the supernatant was
directly subjected to GC analysis. The sugar derivatives
obtained from compounds 1, 2, and 4 showed a single peak (tR
at 21.55 min) comparable with that of a D-glucose derivative,
while 3 showed two peaks (tR at 21.55 and 16.33 min) for
D-glucose and D-xylose derivatives, respectively. Compounds
5 and 6 showed similar peaks for their sugar derivatives at tR
21.55 min (for a D-glucose derivative) and 18.04 min (for a
L-rhamnose derivative). Derivatives obtained for standard
L-glucose and L-xylose had their tR at 22.38 and 19.05 min,
respectively.
20
Yesa n ch in osid e C (3): white amorphous powder, [R]D
+5.9° (c 0.1, 40% CH3CN); IR (KBr) νmax 3389, 2923, 2865,
1630, 1556 cm-1; 1H NMR and 13C NMR (see Tables 1, 2, and
3); API-MS (positive mode, MeOH) m/z 971 [M + Na]+ , 949
[M + H]+, 817 [M - xyl + H]+, 655 [M - xyl - glc + H]+, 493
[M - xyl - 2glc + H]+, 457 [M - xyl - 2glc - H2O + H]+;
APIMS/MS (positive, parent ion m/z 949) 839 [M - xyl + Na]+,
619 [M - xyl - glc - 2H2O + H]+, 475 [M - xyl - 2glc - H2O
+ H]+, 457 [M - xyl - 2glc - 2H2O + H]+, 439 [M - xyl -
2glc - 3H2O + H]+, 421 [M - xyl - 2glc - 4H2O + H]+;
(negative, MeOH/NH4OAc) m/z 1007 [M + OAc]-, 947 [M -
H]-, 875 [M + OAc - xyl]-, 815 [M - xyl - H]-, 653 [M - xyl
- glc - H]-; APIMS/MS (negative, parent ion m/z 947) 947
[M - H]-, 815 [M - xyl - H]-, 653 [M - xyl - glc - H]-, 491
[M - xyl - 2glc - H]-. anal. C 57.32%, H 8.54%, calcd for
C
47H80O19‚2H2O, C 57.11%, H 8.51%.
Yesa n ch in osid e D (4): white amorphous powder, [R]D
20
+13.6° (c 0.1, 40% CH3CN); IR (KBr) νmax 3396, 2931, 1745,
1647, 1556 cm-1; 1H NMR and 13C NMR (see Tables 1, 2, and
3); API-MS (positive mode, MeOH) m/z 865 [M + Na]+, 843
[M + H]+, 823 [M - Ac + Na]+, 685 [M - glc - H2O + Na]+;
APIMS/MS (positive, parent ion m/z 865) 865 [M + Na]+, 703
[M - glc + Na]+, 685 [M - glc - H2O + Na]+, 481 [M - 2glc
- Ac - H2O + Na]+, 463 [M - 2glc - Ac - 2H2O + Na]+;
(negative, MeOH) m/z 841 [M - H]-, 799 [M - Ac-H]-. anal.
C 60.14%, H 8.88%, calcd for C44H74O15‚2H2O, C 59.95%, H
8.85%.
Ack n ow led gm en t. We are cordially grateful to Dr. M. R.
Meselhy, Institute of Natural Medicine, Toyama Medical and
Pharmaceutical University, for his critical comments on the
manuscript. This work was supported in part by a Grant-in-
Aid for Scientific Research (B), No. 11695086 in 1999-2001
from the J apan Society for the Promotion of Science.
20
Yesa n ch in osid e E (5): white amorphous powder, [R]D
Refer en ces a n d Notes
+1.5° (c 0.1, 40% CH3CN); IR (KBr) νmax 3392, 2931, 2874,
1649, 1549 cm-1; 1H NMR and 13C NMR (see Tables 1, 2, and
3); API-MS (positive mode, MeOH) m/z 1131 [M + Na]+, 985
[M - glc + K]+; APIMS/MS (positive, parent ion m/z 1131)
1131 [M + Na]+, 951 [M - glc - H2O + Na]+, 807 [M - 2glc
+ Na]+, 789 [M - 2glc - H2O + Na]+; (negative) m/z 1107 [M
- H]-; APIMS/MS (negative, parent ion m/z 1107) 1107 [M -
H]-, 961 [M - rha - H]-, 945 [M - glc - H]-, 799 [M - glc -
rha - H]-, 783 [M - 2glc - H]-, 765 [M - 2glc - H2O - H]-,
637 [M - 2glc - rha - H]-, 619 [M - 2glc - rha - H2O -
H]-, 475 [M - 3glc - rha - H]-. anal. C 55.76%, H 8.43%,
calcd for C54H92O23‚3H2O, C 55.60%, H 8.40%.
(1) Kumagai, A.; Tanaka, O.; Oura, H. Medicinal Ginseng 2000; Kumagai,
A., Ed.; Kyoritsu Press: Tokyo, 2000; pp 8-29.
(2) Attele, A. S.; Wu, J . A.; Yuan, C. S. Biochem. Pharmacol. 1999, 58,
1685-1693.
(3) Gillis, C. N. Biochem. Pharmacol. 1997, 54, 1-8.
(4) Yoshikawa, M.; Murakami, T.; Yashiro, K.; Yamahara, J .; Matsuda,
H.; Saijoh, R.; Tanaka, O. Chem. Pharm. Bull. 1998, 46, 647-654.
(5) Kinjo, J .; Okawa, M.; Sohno, Y.; Hirakawa, T.; Shii, Y.; Nahara, T.
Chem. Pharm. Bull. 1999, 47, 290-292.
(6) Li, Z.; Guo, Y. Y.; Wu, C. F.; Li, X.; Wang, J . H. J . Pharm. Pharmacol.
1999, 51, 435-440.
(7) Wei, J . X.; Du, Y. C. Panax notoginseng: Modern Scientific Investiga-
tion and Application; Yunnan Science and Technology Press: Kun-
ming, 1993; pp 42-151.
(8) Namba, T. The Encyclopedia of Wakan-Yaku (Traditional Sino-
J apanese Medicines) with Color Pictures; Hoikusha Press: Osaka,
1993; Vol. I, pp 3-4.
20
Yesa n ch in osid e F (6): white amorphous powder, [R]D
+3.3° (c 0.1, 40% CH3CN); IR (KBr) νmax 3394, 2926, 1740,
1648, 1553 cm-1; 1H NMR and 13C NMR (see Tables 1, 2, and
3); API-MS (positive mode, MeOH/NH4OAc) m/z 1173 [M +
Na]+, 971 [M - glc - H2O + H]+; APIMS/MS (positive, parent
ion m/z 1173) 1173 [M + Na]+, 849 [M - 2glc + Na]+, 831 [M
- 2glc - H2O + Na]+; (negative, MeOH/NH4OAc) m/z 1149
[M - H]-, 1107 [M - Ac - H]-, 1089 [M - HOAc - H]-;
APIMS/MS (negative, parent ion m/z 1149) 1107 [M - Ac -
H]-, 1089 [M - HOAc - H]-, 961 [M - rha - Ac - H]-, 945
[M - glc - Ac - H]-, 783 [M - 2glc - Ac - H]-, 781 [M - glc
- rha - HOAc - H]-, 765 [M - 2glc - HOAc - H]-, 637 [M
- 2glc - rha - Ac - H]-, 619 [M - 2glc - rha - HOAc - H]-,
(9) Institute of Materia Medica, Chinese Academy of Medical Sciences;
et al. Zhong Yao Zhi (The Traditional Chinese Medicines); People’s
Medical Publishing House: Beijing, 1979; pp 17-20.
(10) Matsumoto, N.; Tohda, C.; Zou, K.; Komatsu, K. J . Traditional Med.
2001, 18 (Suppl.), 83.
(11) Komatsu, K.; Zhu, S.; Fushimi, H.; Qui, T. K.; Cai, S. Q.; Kadota, S.
Planta Med. 2001, 67, 461-465.
(12) Zhu, S.; Fushimi, H.; Komatsu, K.; Cai, S. Q. The 47th Annual
Meeting of the J apanese Society of Pharmacognosy. Abstract pa-
pers: p 118, 2000 (Tokyo).
(13) Duc, N. M.; Nham, N. T.; Kasai, R.; Ito, A.; Yamasaki, K.; Tanaka,
O. Chem. Pharm. Bull. 1993, 41, 2010-2014.
(14) Namba, T.; Matsushige, K.; Morita, T.; Tanaka, O. Chem. Pharm.
Bull. 1986, 34, 730-738.