Journal of Natural Products
ARTICLE
ꢀ
ESIMS m/z 645 [M ꢀ H] ; HRESIMS m/z 645.4013 (calcd for
’ AUTHOR INFORMATION
C H O , 645.4002).
3
7 57 9
Corresponding Author
*Tel: 86-871-5223177. Fax: 86-871-5150227. E-mail: xdluo@
mail.kib.ac.cn.
Fruticoside E (6): white, amorphous powder; mp 241ꢀ242 °C;
18
D
[
1
R]
ꢀ30.4 (c 0.09, MeOH); IR (KBr) νmax 3432, 2958, 1710,
ꢀ1 1 13
638, 893 cm ; H and C NMR data, see Tables 2 and 3; negative
ꢀ
ESIMS m/z 645 [M ꢀ H] ; HRESIMS m/z 669.3977 (calcd for
C
37
H
58
O
9
Na, 669.3978).
Fruticoside F (7): white, amorphous powder; mp 210ꢀ211 °C;
’
ACKNOWLEDGMENT
18
D
[
1
R]
ꢀ71.1 (c 0.16, MeOH); IR (KBr) ν
3445, 2962, 2937,
max
ꢀ
1 1
13
The authors are grateful to the Ministry of Science and
734, 1641, 888 cm ; H and C NMR data, see Tables 2 and 3; negative
ꢀ
ꢀ
ꢀ
Technology of the P. R. China (2009CB522300, 2007AA021505)
and the fund of State Key Laboratory of Phytochemistry and Plant
Resources in West China for financial support.
FABMS m/z 661 [M ꢀ H] , 662 [M þ 1 ꢀ H] , 663 [M þ 2 ꢀ H] ;
HRESIMS m/z 661.3772 (calcd for C37 S, 661.3774).
Fruticoside G (8): white, amorphous powder; mp 247ꢀ251 °C;
57 8
H O
18
D
[
1
R]
ꢀ72.7 (c 0.16, MeOH); IR (KBr) νmax 3440, 2934, 1710,
ꢀ1 1 13
631 cm ; H and C NMR data, see Tables 2 and 3; negative
ꢀ
ꢀ
ꢀ
’
REFERENCES
FABMS m/z 617 [M ꢀ H] , 618 [M þ 1 ꢀ H] , 619 [M þ 2 ꢀ H] ;
HRESIMS m/z 617.3868 (calcd for C H O S, 617.3875).
(1) Boon, J. J.; Rijpstra, W. I. C.; Lange, F. D.; Leeuw, J. W. D. Nature
36
57
6
Acid Hydrolysis of 4ꢀ8. Compounds 4ꢀ8 (15 mg each) were
refluxed with 10% HClꢀMeOH (20 mL) on a water bath at 60 °C for 8
h, respectively. The reaction mixtures were evaporated to dryness and
1979, 277, 125–127.
(2) Robinson, N.; Eglinton, G.; Brassell, S. C. Nature 1984,
3
08, 439–442.
3) Volkman, J. K.; Barrett, S. M.; Dunstan, G. A.; Jeffrey, S. W. Org.
Geochem. 1993, 20, 7–15.
4) (a) Kokke, W. C. M. C.; Fenical, W.; Djerassi, C. Steroids 1982,
0, 307–318. (b) Robinson, N.; Cranwell, P. A.; Eglinton, G.; Jaworski,
(
2
redissolved in H O, then partitioned with EtOAc, to afford EtOAc and
H O layers. The sugars were compared with authentic samples (L-
2
(
rhamnose and D-quinovose) and identified by TLC using
4
CHCl
3
ꢀMeOH (6:4) as rhamnose (R
f
0.49) in 6 and quinovose (R
O layers were performed by
f
G. H. M. Phytochemistry 1987, 26, 411–421. (c) Kaku, K.; Hiraga, Y. Nat.
Prod. Res. 2003, 17, 263–267.
0.52) in 4, 5, 7, and 8. Purifications of the H
2
preparative TLC, eluted four times with CHCl ꢀMeOHꢀH O
3
2
(
5) (a) Yin, S. W.; Shi, Y. P.; Li, X. M.; Wang, B. G. Helv. Chim. Acta
006, 89, 567–572. (b) Sekhar, V. C.; Rao, C. B.; Rao, D. V.; Sarvani, B.;
Lakshmi, D. K. M. Asian J. Chem. 2004, 16, 572–576.
6) (a) Mazur, Y.; Weizmann, A.; Sondheimer, F. J. Am. Chem. Soc.
18
(
70:30:1), to afford L-rhamnose (R
f
0.56, [R]
D
þ11.4; H
2
O) in 6
2
O) in 4,
2
18
and L-quinovose (R
5
f
0.62, [R]
D
ꢀ9.3, ꢀ10.5, ꢀ8.9, ꢀ6.9; H
, 7, and 8, respectively. The EtOAc layers, monitored by HPTLC on
(
silica gel GF254 plates using CHCl ꢀMeOH (10:1) and CHCl ꢀMe
3
3
2-
1958, 80, 1007–1008. (b) Djerassi, C.; Krakower, G. W.; Lemin, A. J.;
Liang, H. L.; Mills, J. S.; Villotti, R. J. Am. Chem. Soc. 1958,
80, 6284–6292. (c) Schreiber, K.; Osske, G. Tetrahedron 1964,
20, 2575–2584. (d) Osske, G.; Schreiber, K. Tetrahedron 1965,
21, 1559–1566. (e) Toshihiro, A.; Yoshihiro, H.; Glenn, W. P.; Naoto,
S.; Toshitake, T. Phytochemistry 1992, 31, 1759–1763. (f) Suhag, P.;
Bharati; Mahla, M.; Singh, R.; Kalidhar, S. B. J. Indian Chem. Soc. 2002,
CO (5:1), showed several decomposition products.
Fruticoside D (5) Converted to Fruticoside F (7). To a
solution of 5 (32.3 mg, 0.05 mmol) in DMF (1 mL) was added
carbonyl diimidazole (16.3 mg, 0.1 mmol), and the reaction mixtures
were stirred at 25 °C for 6 h. NaSH (13.5 mg, 0.24 mmol) was then
added and stirring continued at 25 °C for 20 h. The reaction mixtures
were poured into aqueous 2 M HCl (20 mL) cooled in an ice bath. The
resulting precipitate was filtered and dried in vacuo to give 7 (8.7 mg,
7
9, 548–549. (g) Klink, G.; Dreier, F.; Buchs, A.; G €u la c- ar, F. O. Org.
Geochem. 1992, 18, 757–763.
7) Qiu, H. X.; Huang, S. M.; Zhang, Y. T. Flora of China:
(
2
6.9%).
Euphorbiaceae; Qiu, H. X., Ed.; Science Press: Beijing, 1996; Vol. 44,
Chapter 1, pp 178ꢀ184.
Cytotoxicity Assay. Five human cancer cell lines, human mye-
loid leukemia HL-60, hepatocellular carcinoma SMMC-7721, lung
cancer A-549, breast cancer MCF-7, and colon cancer SW480, were
used in the cytotoxic assay. Cells were cultured in DMEM medium
(8) Lee, S. S.; Shy, S. N.; Liu, K. C. S. Phytochemistry 1997,
46, 547–554.
(9) Jagadeesh, S. G.; Krupadanam, G. L. D.; Sirmannarayana, G.
(
(
Hyclone, USA), supplemented with 10% fetal bovine serum
Indian J. Chem. 2000, 39B, 396–398.
(10) Guo, S.; Tang, Y. P.; Duan, J. A.; Su, S. L.; Ding, W. Chin. Chem.
Lett. 2009, 20, 197–200.
(11) Jiri, K.; Jiri, L.; Alean, F.; Milos, B.; Jiri, P.; Stanislav, H.; Alois, V.
Collect. Czech. Chem. Commun. 1989, 54, 413–429.
(12) Zhang, W. H.; Liu, W. K.; Che, C. T. Chem. Pharm. Bull. 2003,
Hyclone, USA), in 5% CO at 37 °C. The cytotoxicity assay was
2
performed according to the MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-
diphenyl tetrazolium bromide) method in 96-well microplates.
3
3
Briefly, 100 μL of adherent cells was seeded into each well of 96-well
cell culture plates and allowed to adhere for 12 h before addition of
test compounds, while suspended cells were seeded just before drug
5
1, 1009–1011.
13) Alejandro, F. B.; Oltra, J. E.; Juan, A. P.; David, J.; Eulalia, O.
J. Nat. Prod. 1998, 61, 1491–1496.
14) Fu, L. W.; Zhang, S. J.; Li, N.; Wang, J. L.; Zhao, M.; Sakai, J.;
5
(
addition with initial density of 1 ꢁ 10 cells/mL. Each tumor cell line
was exposed to the test compound at concentrations of 0.064, 0.32,
(
1
.6, 8, and 40 μM in triplicates for 48 h, with cisplatin (Sigma, USA) as
Hasegawa, T.; Mitsui, T.; Kataoka, T; Oka, S.; Kiuchi, M.; Hirose, K.;
Ando, M. J. Nat. Prod. 2005, 68, 198–206.
(15) Wang, T. M.; Hojo, T.; Ran, F. X.; Wang, R. F.; Wang, R. Q.;
Chen, H. B.; Cui, J. R.; Shang, M. Y.; Cai, S. Q. J. Nat. Prod. 2007,
a positive control. After compound treatment, cell viability was
detected and a cell growth curve was graphed. IC50 values were
3
4
calculated by Reed and Muench’s method.
7
0, 1429–1433.
16) (a) Leon, M. L. J. Org. Chem. 1972, 37, 4386–4391. (b) Emmanuel,
Z.; Nelson, K. R.; Hudson, C. S. J. Am. Chem. Soc. 1951, 73, 4714–4716.
17) Kocharova, N. A.; Ovchinnikova, O. G.; Toukach, F. V.; Torzeska,
A.; Shashkov, A. S.; Knirel, Y. A.; Rozalski, A. Carbohydr. Res. 2005,
40, 1419–1423.
(
’
ASSOCIATED CONTENT
Supporting Information. 1D and 2D NMR, MS, and IR
(
S
b
spectra of breynceanothanolic acid (1) and fruticosides AꢀG
3
(
2ꢀ8). These materials are available free of charge via the
(18) (a) Eskander, J.; Lavaud, C.; Abdel-khalik, S. M.; Soliman, H. S. M.;
Mahmoud, I. I.; Long, C. J. Nat. Prod. 2005, 68, 832–841. (b) Tran, Q. L.;
Internet at http://pubs.acs.org.
1
167
dx.doi.org/10.1021/np2000914 |J. Nat. Prod. 2011, 74, 1161–1168