Triterpenoid glycosides from the stems of Gordonia kwangsiensis

Article abstract of DOI:10.1016/j.phytochem.2012.08.019

Eleven oleanane-type triterpenoid glycosides, named gordonsaponins A-K, were isolated from the stems of Gordonia kwangsiensis. Their structures were elucidated by spectroscopic and chemical methods. The cytotoxic activities of all eleven were evaluated against five human tumor cell lines (HCT-8, Bel-7402, BGC-823, A549, and A2780), with only one having activity against all tested cell lines, with IC₅₀ values ranging from 0.1 to 2.41 μM.

Full text of DOI:10.1016/j.phytochem.2012.08.019

Phytochemistry 85 (2013) 167–174
Contents lists available at SciVerse ScienceDirect
Phytochemistry
journal homepage: www.elsevier.com/locate/phytochem
Triterpenoid glycosides from the stems of Gordonia kwangsiensis
⇑
Hui-Zheng Fu, Chuang-Jun Li, Jing-Zhi Yang, Xiao-Guang Chen, Dong-Ming Zhang
State Key Laboratory of Bioactive Substance and Function of Natural Medicines, Institute of Materia Medica,
Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing 100050, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 1 March 2012
Received in revised form 22 May 2012
Available online 23 September 2012
Eleven oleanane-type triterpenoid glycosides, named gordonsaponins AꢀK, were isolated from the stems
of Gordonia kwangsiensis. Their structures were elucidated by spectroscopic and chemical methods. The
cytotoxic activities of all eleven were evaluated against five human tumor cell lines (HCT-8, Bel-7402,
BGC-823, A549, and A2780), with only one having activity against all tested cell lines, with IC50 values
ranging from 0.1 to 2.41 lM.
Keywords:
Ó 2012 Elsevier Ltd. All rights reserved.
Gordonia kwangsiensis
Theaceae
Triterpenoid glycosides
Gordonsaponins AꢀK
Cytotoxic activity
1
. Introduction
The genus Gordonia (Theaceae) includes 40 species with ubiqui-
n-BuOH-soluble portion showed selective cytotoxicities for HCT-8
(
IC50 = 10.78
n-BuOH-soluble portion was fractionated by silica gel column
chromatography to give fractions A eluted with
ꢀA10. Fraction A
O mixture from the D101 macroporous resin chromatog-
lM) and Bel-7402 (IC50 = 35.42 lM) cell lines. The
tous distribution around the world. Of these Gordonia kwangsiensis
chang is distributed widely in the Guangxi, Guizhou, and Yunnan
Provinces of the People’s Republic of China (Board Editorial Board,
the Chinese Academy of Sciences, 1998). Previous phytochemical
studies on Gordonia species showed that plants of this genus are rich
in triterpenoids (Herath and Athukoralage, 1998, 2000; Hearth et al.,
1
5
EtOHꢀH
2
raphy led to isolation of 11 triterpenoid saponins. Their structures
were elucidated by extensive spectroscopic chemical methods
1
13
including 1D ( H and C) and 2D NMR (HSQC, HMBC, TOCSY,
and NOESY) experiments as well as ESIMS analysis.
1
999, 2000, 2001), steroids (Herath et al., 1999), tannins (Wang
et al., 2001), and several other components (Athukoralage et al.,
001) were also isolated from these plants. Some of these
Compound 1 was obtained as a white, amorphous powder. The
ꢀ1
IR spectrum of
1
showed hydroxy (3402 cm ), carbonyl
ꢀ
1
ꢀ1
2
(1678 cm ), and
a,b-unsaturated carbonyl (1080 cm ) absorp-
substances exhibit apoptosis-inducing (Wang et al., 2001) and anti-
fungal (Athukoralage et al., 2001) activities. In the course of a contin-
uing search for new biologically active compounds from plant
resources, the n-BuOH part of the 95% EtOH extract of the stems of
G. kwangsiensis was found to exhibit selective cytotoxicities for
HCT-8 and Bel-7402 cell lines. Until now, there were no reports on
its chemical constituents and bioactivities. Studies focusing on
biologically significant anticancer properties led to the isolation of
tion signals. The molecular formula C53
by HRESIMS (m/z 1113.5473 [M + Na] , calcd. for 1113.5452) and
supported by the NMR spectroscopic data. The H NMR spectrum
H
86
O
23 was determined
+
1
of 1 in pyridine-d
1.03, 1.07, 1.10, 1.21, and 1.83). Additional resonances observed in-
cluded those ascribed to an olefinic proton at d 5.34 (1H, br s), two
oxymethylene protons at d 3.59 and 3.72 (1H each, d, J = 11.0 Hz),
two oxymethine protons at d 3.24 (1H, dd, J = 11.5, 4.5 Hz) and
4.61 (1H, m), and four anomeric proton signals at d 4.85 (1H, d,
J = 7.5 Hz), 5.05 (1H, d, J = 7.5 Hz), 5.70 (1H, d, J = 8.0 Hz), and
5 H
showed seven methyl signals (d 0.80, 0.91,
H
H
H
1
1 triterpenoid saponins. Reported herein are the isolation, struc-
H
tural elucidation, and biological activity of these compounds.
6
.02 (1H, d, J = 8.0 Hz) correlated in the HSQC spectrum with four
13
anomeric carbons at d
C
105.4, 107.5, 101.9, and 102.2 in the
C
1
3
2
. Results and discussion
NMR spectrum, respectively (Table 1). The C NMR spectrum of
displayed 53 carbon signals, of which 23 were assigned to the su-
1
The 95% EtOH extract of the stems of G. kwangsiensis was
gar moieties and the remaining 30 to the aglycone. These data sug-
gested that the aglycone part of 1 was likely to be a pentacyclic
triterpene with two hydroxyl groups and a trisubstituted double
bond. Comparison of the NMR spectroscopic data of 1 (Table 1)
with those of primulagenin A (Akai et al., 1985) demonstrated that
partitioned with CHCl
3
,
EtOAc, n-BuOH, successively. The
⇑
Corresponding author. Tel.: +86 10 63165227; fax: +86 10 63165227.
E-mail address: zhangdm@imm.ac.cn (D.-M. Zhang).
0
031-9422/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.phytochem.2012.08.019

1
68
H.-Z. Fu et al. / Phytochemistry 85 (2013) 167–174
Table 1
5 5
NMR spectroscopic data (500 MHz, C D N) for compounds 1, 2, 9, and 11.
1
2
9
11
d
H
(J in Hz)
d
C
d
H
(J in Hz)
d
C
d
H
(J in Hz)
d
C
d
H
(J in Hz)
d
C
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
2
3
38.7
26.3
89.3
39.8
55.5
18.2
33.3
39.8
46.8
36.6
23.6
123.1
145.0
42.2
34.6
74.0
40.7
41.8
48.1
38.7
26.6
89.4
39.5
55.5
18.7
30.9
38.9
47.2
36.9
23.9
123.1
145.9
47.9
67.5
78.6
41.0
43.1
47.9
38.8
26.5
89.4
39.5
55.4
18.7
36.9
39.4
47.0
36.6
23.9
125.3
143.6
47.1
67.5
75.0
45.4
41.4
47.6
38.7
26.5
89.6
39.5
55.7
18.4
35.7
40.0
46.8
36.2
23.8
123.9
142.7
40.9
34.8
68.6
46.8
41.6
47.1
3.24, dd (11.5, 4.5)
0.74, m
3.24, dd (11.5, 4.5)
0.79, m
3.20, br d (11.5)
0.80, m
3.19, dd (11.5, 5.0)
0.79, m
1.70, m
1.69, m
1.68, m
1.69, m
0
1
2
3
4
5
6
7
1.83, m
5.34, br s
1.84, m
5.44, br s
1.78, m
5.48, br s
1.86, m
5.42, br s
a
2.18, m
4.61, m
4.38, m
4.54, m
4.21, m
4.52, m
1.88, m
4.32, m
8
2.49, br d (13.0)
2.72, t (13.0)
1.30, m
2.43, br d (12.0)
2.71, m
1.35, m
2.81, br d (11.5)
3.00, t (13.0)
1.68, m
3.08, m
3.08, m
1.69, m
9a
9b
0
1
2
3
4
5
6
31.1
36.9
30.3
24.6
16.5
15.5
16.8
27.2
69.9
31.2
36.7
31.0
27.9
17.5
15.8
16.7
20.9
69.5
33.4
24.5
33.1
79.1
73.5
27.9
16.7
15.7
17.5
20.6
63.6
36.7
79.3
73.4
28.0
16.7
15.6
16.8
27.5
63.5
1.22, m
2.27, m
1.10, s
1.07, s
0.80, s
0.91, s
1.83, s
3.72, d (11.0)
3.59, d (11.0)
1.03, s
1.31, m
2.27, m
1.21, s
1.08, s
0.83, s
1.04, s
1.82, s
3.79, d (10.5)
3.60, d (10.5)
1.04, s
6.58, d (10.0)
6.15, d (10.0)
1.31, s
1.10, s
0.80, s
0.98, s
1.84, s
3.74, d (10.5)
3.49, d (10.5)
0.99, s
6.58, d (10.0)
6.30, d (10.0)
1.25, s
1.09, s
0.80, s
0.84, s
1.83, s
3.67, d (10.0)
3.43, d (10.0)
1.07, s
7
8a
8b
9
33.0
27.7
33.2
24.8
29.4
19.5
0
1.21, s
1.10, s
1.27, s
1.31, s
Ang
0
1
168.1
129.0
136.5
15.7
168.2
129.2
137.1
15.8
0
2
0
3
5.81, q (6.5)
2.02, d (6.5)
1.79, s
5.93, q (7.0)
2.06, d (7.0)
2.08, s
0
4
0
5
20.1
20.8
Sugar (C-3) GlcA
1
2
3
4
5
6
4.85, d (7.5)
4.67, t (8.5)
4.43, m
4.38, m
4.11, m
105.4
78.1
84.7
70.9
76.8
171.7
4.85, d (7.0)
4.65, t (9.0)
4.45, m
4.46, m
4.49, m
105.6
78.3
84.9
71.1
77.0
4.88, d (7.5)
4.65, t (8.5)
4.45, m
4.53, m
4.50, m
105.5
78.8
84.8
71.0
76.9
171.9
4.87, d (7.0)
4.61, t (8.5)
4.40, m
4.54, m
4.55, m
105.4
78.9
83.8
71.3
77.3
176.1
171.9
Xyl (1 ? 3) GlcA
1
2
3
4
5
5.70, d (8.0)
4.52, dd (8.0, 8.5)
4.24, t (8.5)
4.50, m
101.9
83.7
74.9
70.3
67.4
5.70, d (7.5)
4.50, dd (7.5, 8.5)
4.24, t (8.5)
4.37, m
3.44, t (13.0)
4.48, m
101.8
83.9
75.1
70.5
67.6
5.69, d (7.5)
4.49, m
4.09, t (8.0)
4.27, m
3.41, t (11.5)
4.24, m
101.8
83.5
77.2
70.7
67.5
3.43, t (13.5)
4.39, m
Glc (1 ? 2) Xyl
1
2
3
4
5
6
5.05, d (7.5)
4.24, t (7.5)
4.01, t (8.5)
4.48, m
4.32, m
4.35, m
107.5
74.9
78.2
69.4
76.3
61.5
5.05, d (8.0)
4.24, t (8.0)
4.04, t (8.5)
4.47, m
4.31, m
4.34, m
107.6
75.1
78.4
69.6
76.5
61.7
5.07, d (7.5)
4.25, dd (7.5, 8.5)
4.00, t (8.5)
4.51, m
4.24, m
4.34, m
107.4
75.0
78.3
70.1
76.0
61.7
Gal (1 ? 2) GlcA
1
2
3
4
5
6
5.86, d (7.5)
4.49, m
4.47, m
4.47, m
4.35, m
103.2
73.7
78.3
69.6
76.3
61.9
5.70, d (7.0)
4.49, m
4.53, m
4.55, m
4.27, m
103.4
73.7
75.0
70.1
76.4
61.8
4.44, m
4.43, m
0
Glc (1 ? 2) GlcA
1
2
6.02, d (8.0)
4.12, dd (8.0, 8.5)
102.2
72.6
6.02, d (7.5)
4.10, m
102.4
72.8

H.-Z. Fu et al. / Phytochemistry 85 (2013) 167–174
169
Table 1 (continued)
1
2
9
11
d
H
(J in Hz)
d
C
d
H
(J in Hz)
d
C
d
H
(J in Hz)
d
C
d
H
(J in Hz)
d
C
3
4
5
6
4.09, t (8.5)
4.48, m
4.47, m
77.0
77.1
78.0
63.4
4.09, m
4.47, m
4.44, m
4.49, m
4.31, m
77.2
77.1
78.2
63.6
4.50, m
4.30, m
Ara (1 ? 3) GlcA
1
2
3
4
5
5.70, d (7.0)
4.55, m
4.48, m
4.29, m
3.72, t (10.0)
101.7
82.0
73.6
68.3
65.6
4.39, m
Xyl (1 ? 2) Ara
1
2
3
4
5
5.02, d (7.5)
4.17, m
4.03, m
4.22, m
3.72, t (7.5)
106.7
75.7
78.2
70.6
67.4
4.38, m
21-OAc
1
2
170.8
21.2
170.8
20.0
2.11, s
1.91, s
a
Overlapped with other signals.
it belongs to the oleanane series. The assignment of hydroxyl group
C-3 was confirmed from the HMBC correlations between H-1, H-2,
copyranosyl-(1 ? 2)]-b-D-glucuronopyranoside. The relative
configuration of 1 was deduced by analysis of the NOESY spectrum,
which showed NOE correlations between the following proton
pairs: H-3/H-5 and H-16/H-26. Thus, compound 1 was determined
H-23, H-24 and C-3. The two oxymethylene proton signals at d
H
3
6
1
.59 and 3.72, which correlated with the carbon resonance at d
9.9 in the HSQC spectrum, showed HMBC correlations with C-
6, C-17, C-18, and C-22, justifying its assignment to C-28. The
C
as 3-O-b-
[b- -glucopyranosyl-(1 ? 2)]-b-
ene-16 ,28-diol, and has been named gordonsaponin A.
D
-glucopyranosyl-(1 ? 2)-b-
D-xylopyranosyl-(1 ? 3)-
D
D
-glucuronopyranosyl-olean-12-
HMBC correlations for H-9, H-10, H-18 with C-12, and H-10, H-
8, H -27 with C-13 suggested the position of double bone in the
triterpene core. A series of HMBC correlations from H -29 to
C-19, C-20, C-21, and C-30, from H -30 to C-19, C-20, C-21, and
a
1
3
Compound 2 was isolated as a white, amorphous powder. The
+
3
HRESIMS peak at m/z 1129.5423 [M + Na] indicated the molecular
3
86
formula of 2 to be C53H O24, with one oxygen atom more than that
+
C-29 allowed the connection of C-19, C-21, C-29, and C-30 to the
quaternary carbon C-20 demonstrated that C-29 and C-30 were
connected to the same carbon (C-20). From the foregoing evi-
dences it was concluded that 1 possessed a 28-hydroxyolean-
of 1 (1113 [M + Na] ). The structure of the sugar chain was deter-
1
mined to be the same as that of 1 by comparison of their H and
1
3
C NMR spectroscopic data (Table 1). However, detailed compari-
son of the NMR data of 2 and 1 indicated that signals of an oxyme-
1
4
4
2-ene aglycone. In addition, the oxymethine proton signal at d
.61 (1H, m), which correlated with C-15 (d 34.6) and C-17 (d
0.7) in the HMBC spectrum, could be assigned to H-16. Compari-
H
thine (CH-15) of 2 replaced those of the methylene (CH
and that C-14 and C-16 of 2 were deshielded by
4.6 ppm as compared to those of 1, respectively. These data sug-
gested that 2 is a 15-oxygenated derivative of 1, which was further
confirmed by a HMBC experiment on 2. In the HMBC spectrum of 2,
2
-15) of 1
5.7 and
C
C
D
d
C
son of the NMR spectroscopic data of 1 with those of aesculioside
G1 (Yuan et al., 2012) established it to be a glycoside of an oxygen-
ated 28-hydroxyolean-12-ene aglycone (Table 1).
correlations from both H
firmed that the additional hydroxyl group is located at C-15. In the
NOESY spectrum of 2, correlations between H-15 with H -26 and
-28, together with correlations between H-16 and H -28, were
used to show that both hydroxyl groups at C-15 and C-16 have
an -oriented (Lu et al., 2000). Thus, compound 2 (gordonsaponin
B) was elucidated as 3-O-b- -glucopyranosyl-(1 ? 2)-b- -xylopyr-
anosyl-(1 ? 3)-[b- -glucopyranosyl-(1 ? 2)]-b- -glucuronopyr-
anosyl-olean-12-ene-15 ,16 ,28-triol.
Compound 3 was isolated as a white, amorphous powder. Its
molecular formula, C58 26, was determined by HRESIMS (m/z
3 C
-27 and H-16 to C-15 (d 67.5 ppm) con-
Acid hydrolysis of 1 with 2 M HCl afforded monosaccharides,
which were identified by GC analysis of their trimethylsilyl
teine derivatives (Fu et al., 2011) as -glucuronic acid, -xylose,
and -glucose in a ratio of 1:1:2. On the basis of the coupling con-
stants of anomeric protons and the chemical shifts of the anomeric
carbons, the anomeric configurations of the sugar moieties were
determined as b for glucuronic acid, xylcose, and glucose moieties.
The sequence of the glycosidic chains in 1 was determined by the
analysis of the 2D NMR spectroscopic data. The proton and proton-
ated carbon signals in the NMR spectra of 1 were assigned
unequivocally (Table 1) on the basis of TOCSY and HSQC
L-cys-
3
D
D
H
2
2
D
a
D
D
D
D
a
a
92
H O
+
1227.5816 [M + Na] , calcd. for 1227.5823). The IR and NMR data
spectroscopic analysis. HMBC correlation from GlcA-H1 (d
to C-3 (d 89.3) confirmed that the b- -glucuronopyranosyl unit
is located at C-3. Long-range correlations observed between the
H
4.85)
of 3 were almost identical to those of 2 (see Section 4), except
C
D
for signal corresponding to an additional angeloyl group [d
H
1.82
(3H, s), 2.02 (3H, d, J = 7.0 Hz), and 5.83 (1H, q, J = 7.0 Hz); d
C
1
0
13
H NMR resonances at d
at d 78.1 (GlcA-C-2), between d
C-3), and between d 5.05 (Glc-H-1) and d
indicated that the tetrasaccharide residue at C-3 of aglycone is
b- -glucopyranosyl-(1 ? 2)-b- -xylopyranosyl-(1 ? 3)-[b- -glu-
H
6.02 (Glc -H-1) and the C NMR signals
5.70 (Xyl-H-1) and d 84.7 (GlcA-
83.7 (Xyl-C-2)
167.9, 136.4, 129.3, 20.8, and 15.8] in the NMR spectrum of 3.
0
C
H
C
Additionally, HMBC correlations from H-22 (d
H
6.19) to C-1 (d
C
H
C
167.9) indicated unambiguously that the angeloyloxy ester group
is attached to C-22 of the aglycone. In the NOESY spectrum of 3,
a correlation between H-22 and H-18 indicated that the hydroxy
D
D
D

1
70
H.-Z. Fu et al. / Phytochemistry 85 (2013) 167–174
+
group at C-22 is an
C) was elucidated as 3-O-b-
anosyl-(1 ? 3)-[b- -glucopyranosyl-(1 ? 2)]-b-
anosyl-22 -angeloyloxyolean-12-ene-15 ,16 ,28-triol.
Compound 4 gave the same molecular formula as 1, namely,
a
-oriented. Thus, compound 3 (gordonsaponin
-glucopyranosyl-(1 ? 2)- -L-xylopyr-
-glucuronopyr-
of 7 (1211 [M + Na] ). The IR and NMR spectroscopic data of 8 were
almost identical to those of 7 (see Section 4). However, detailed NMR
D
a
D
D
analysies showed an additional hydroxy group at C-15 (d
C
a
a
a
67.4 ppm). These data suggested that 8 is a 15-oxygenated deriva-
tive of 7, which was further confirmed by HMBC and NOESY exper-
iments on 8. Thus, compound 8 (gordonsaponin H) was elucidatedas
+
C
53
H
86
O
23, as deduced by HRESIMS (m/z 1113.5466 [M + Na] ,
calcd. for 1113.5452). Acid hydrolysis of 4 afforded -glucuronic
acid, -xylose, -galactose, and -glucose in a ratio of 1:1:1:1
D
3-O-b-
galactopyranosyl-(1 ? 2)]-b-
oxyolean 12-ene-15 ,16 ,28-triol.
Compound 9 was isolated as a white, amorphous powder. The
molecular formula, C60 28, was determined by HRESIMS (m/z
D
-glucopyranosyl-(1 ? 2)-b-
D
-xylopyranosyl-(1 ? 3)-[b-
D-
D
D
D
D
-glucuronopyranosyl-22
a
-angeloyl-
through GC analysis. The NMR spectroscopic data of compound 4
were almost identical with those of 1 except that the glucose in 1
was replaced by a galactose moiety in 4 (see Section 4). The connec-
tivity for the sugar residues was further confirmed from the follow-
a
a
94
H O
1285.5797 [M + Na]+, calcd. for 1285.5824). The IR and NMR spec-
troscopic data of 9 were almost identical to those of 8 (Table 1), ex-
cept for an additional acetyl group [d 2.11 (3H, s); d 170.8 and
H C
21.2] in the NMR spectrum of 9. These data suggested that 9 is
an acetyl derivative of 8, which was confirmed by appropriate 2D
NMR experiments on 9. In the 1H NMR spectrum of 9, H-21 was
ing HMBC correlations: GlcA-H-1 (d
Xyl-H-1 (d 5.68)/GlcA-C-3 (d 84.7), Glc-H-1 (d
83.5), and Gal-H-1 (d 5.85)/GlcA-C-2 (d
compound 4 (gordonsaponin
pyranosyl-(1 ? 2)-b- -xylopyranosyl-(1 ? 3)-[b-
anosyl-(1 ? 2)]-b- -glucuronopyranosyl-olean-12-ene-15
H C
4.87)/aglycone-C-3 (d 89.5),
H
C
H
5.06)/Xyl-C-3
78.9). Thus,
(d
C
H
C
D
) was elucidated as 3-O-b-
-galactopyr-
,16
D-gluco-
D
D
D
a
a
,
shielded by
droxyl group is located at C-21 (d
trum of 9, a long-range correlation from H-21 (d
carbonyl carbon (d 170.8) of the acetyl unit confirmed that the
D
d
H
3.79 ppm as compared to 8, indicating that the hy-
79.1) in 9. In the HMBC spec-
6.58) to the
2
8-triol.
C
Compound 5 gave the same molecular formula as 2, namely,
H
+
C
53
H
86
O
24, as deduced by HRESIMS (m/z 1129.5411 [M + Na] , calcd.
-glucuronic acid, b-
-galactose in a ratio of 1:1:2 through GC analysis. The
C
for 1129.5401). Acid hydrolysis of 5 afforded
xylose, and b-
D
D
-
acetyl unit is attached to C-21. The vicinal coupling constant
(10.0 Hz) between H-21 and H-22 indicated their trans-diaxial ori-
entation, which was confirmed by NOESY cross-peaks of H-22/
H2-28/H3-30 and H-21/H-19
(gordonsaponin I) was elucidated as 3-O-b-
(1 ? 2)-b- -xylopyranosyl-(1 ? 3)-[b- -galactopyranosyl-(1 ? 2)]
-b- -glucuronopyranosyl-21b-acetyl-22 -angeloyloxyolean 12-
ene-15 ,16 ,28-triol.
D
NMR spectroscopic data of compound 5 were similar to those of 2
except that the glucose in 2 was replaced by a galactose in 5 (see Sec-
a
/H3-27. Thus, compound
9
tion 4). In addition, the
from the HMBC correlation between the H-1 (d
and C-2 (d 78.6) of GlcA. Thus, compound 5 (gordonsaponin E)
was determined as 3-O-b- -glucopyranosyl-(1 ? 2)-b- -xylopyr-
anosyl-(1 ? 3)-[b- -galactopyranosyl-(1 ? 2)]-b- -glucuronopyr-
anosyl-olean-12-ene-16 ,28-diol.
Compound 6 was isolated as a white, amorphous powder. The
molecular formula C55 25 was determined by HRESIMS (m/z
D
-galactose in 5 was assigned to C-2 of GlcA
D
-glucopyranosyl-
H
5.85) of galactose
D
D
C
D
a
D
D
a
a
D
D
Compound 10 was obtained as a white, amorphous power, and
its positive-ion HRESIMS gave a quasimolecular ion peak at m/z
1327.5945 [M + Na] , which indicated the molecular formula to
a
+
H
88
O
be C62
NMR spectroscopic data of 10 were almost identical to those of 9
(see Section 4), except for an additional signals [d 2.01 (3H, s);
170.3 and 20.7] assignable to an acetyl group in the NMR spec-
96 96
H O29 (calcd. for C62H O29Na, m/z 1327.5929). The IR and
+
1
1
171.5520 [M + Na] , calcd. for 1171.5507). Comparison of the H
and C NMR spectroscopic data of 6 with those of 4 indicated that
1
3
H
the signals of their sugar moieties were superimposable, suggesting
d
C
1
13
the sugar structure at C-3 was the same as that in 4. The H and
NMR spectroscopic data of the aglycone moiety in 6 were similar to
those of 4 (see Section 4), except for additional resonances [d 2.11
3H, s); d 169.7 and 21.8] assignable to an acetyl group in the
C
trum of 10. These data suggested that 10 is an acetyl derivative of
9, which was confirmed by appropriate 2D NMR experiments on
10. In the HMBC spectrum of 10, long-range correlations were ob-
H
(
C
served between H-16 (d
170.3), between H-21 (d
170.8), and between H-22 (d
(d 167.5) indicated the two acetyl groups and the angeloyloxy es-
ter group are attached to C-16, C-21, and C-22, respectively. In the
NOESY spectrum of 10, correlations between H-16 and H -28 and
-26 proved the acetyloxy at C-16 possesses an -orientation.
Thus, compound 10 (gordonsaponin J) was elucidated as 3-O-b-
-glucopyranosyl-(1 ? 2)-b- -xylopyranosyl-(1 ? 3)-[b- -galacto-
pyranosyl-(1 ? 2)] -b- -glucuronopyranosyl-16 ,21b- iacetyl-22
-angeloyloxyolean 12-ene-15 ,28-diol.
The molecular formula of 11, C59 26, was indicated from the
HRESIMS peak at m/z 1239.5761 [M + Na] . The NMR data (Table 1)
analysis of 11 indicated that 11 contained the same aglycone, the
structure of sugar chain, and angeloyloxy ester group as gordono-
side I, which has been reported previously (Fu et al., 2011). The
only difference between 11 and gordonoside I is that there is an
H
4.48) and acetyl carbonyl carbon (d
C
NMR spectrum of 6. In the HMBC spectrum of 6, HMBC correlation
H
5.79) and acetyl carbonyl carbon (d
C
0
from H-22 (d
H
4.53) to C-1 (d
C
169.7) indicated unambiguously that
H
6.23) and angeloyl carbonyl carbon
the acetyl group is attached to C-22 of the aglycone. In the NOESY
spectrum of 6, a correlation between H-22 and H-18 indicated that
C
the hydroxy group at C-22 is an
a
-oriented. Thus, compound 6
gordonsaponin F) was determined as 3-O-b- -glucopyranosyl-
1 ? 2)-b- -xylopyranosyl-(1 ? 3)-[b- -galactopyranosyl-(1 ? 2)]-
-glucuronopyranosyl-22 -acetoxyolean-12-ene-16 ,28-diol.
Compound 7 had the molecular formula C58 25, as deduced
from the HRESIMS (m/z 1211.5805 [M + Na] , calcd. for
2
(
(
D
H
3
a
D
D
b-D
a
a
D
D
D
H
92
O
D
a
D
+
a
a
1
211.5820). The NMR spectroscopic data of 7 resembled those of
, except that the acetyl group [d 2.11 (3H, s); d 169.7 and 21.8]
1.94 (3H, s), 2.09 (3H,
d, J = 6.5 Hz), and 5.87 (1H, q, J = 6.5 Hz); d 168.0, 136.5, 129.3,
0.9, and 15.8] in 7 (see Section 4). In the HMBC spectrum of 7,
92
H O
+
6
H
C
in 6 was replaced by an angeloyl group [d
H
C
2
0
H C
HMBC correlations from H-22 (d 6.21) to C-1 (d 168.0) indicated
unambiguously that the angeloyloxy ester group is attached to C-22
H C
additional signals [d 1.91 (3H, s); d 170.8 and 20.0] assignable
of the aglycone. In the NOESY spectrum of 7, a correlation between
to an acetyl group in the NMR spectrum of 11. These data sug-
gested that 11 is an acetyl derivative of gordonoside I, which was
confirmed by appropriate 2D NMR experiments on 11. Acid hydro-
lysis of 11 afforded D-glucuronic acid, L-arabinose, D-xylose, and D-
galactose in a ratio of 1:1:1:1 through GC analysis. In the HMBC
H-22 and H-18 indicated that the hydroxy group at C-22 is an
ented. Thus, compound 7 (gordonsaponin G) was determined as 3-O-
b- -glucopyranosyl-(1 ? 2)-b- -xylopyranosyl-(1 ? 3)-[b- -galac-
topyranosyl-(1 ? 2)]-b- -glucuronopyranosyl-22 -angeloyloxyole-
an-12-ene-16 ,28-diol.
a-ori-
D
D
D
D
a
a
spectrum of 11, long-range correlations were observed between
Compound 8 was isolated as a white, amorphous powder. The
HRESIMS peak at m/z 1227.5795 [M + Na] indicated the molecular
formula of 8 to be C58H O26, with one oxygen atom more than that
92
H-21 (d
H-22 (d
the acetyl group and the angeloyloxy ester group are attached to
H
6.58) and acetyl carbonyl carbon (d
6.30) and angeloyl carbonyl carbon (d
C
170.8), and between
+
H
C
168.2) indicated

H.-Z. Fu et al. / Phytochemistry 85 (2013) 167–174
171
C-21 and C-22, respectively. The vicinal coupling constant
10.0 Hz) between H-21 and H-22 indicated their trans-diaxial
orientation, which was confirmed by NOESY cross-peaks of H-22/
-28/H -30 and H-21/H-19 /H -27. Thus, compound 11 (gordon-
saponin K) was elucidated as 3-O-b- -xylopyranosyl-(1 ? 2)- -L-
arabinopyranosyl-(1 ? 3)-[b- -galactopyranosyl-(1 ? 2)]-b-
glucuronopyranosyl-21b-acetyl-22 -angeloyloxyolean-12-ene-
,28-diol.
Compounds 1–11 were evaluated for their cytotoxic activities
individually partitioned with CHCl
3
(5 ꢁ 2500 mL), EtOAc
(
(5 ꢁ 2400 mL), and n-BuOH (5 ꢁ 2000 mL), respectively. After
removing the solvent, the n-BuOH-soluble portion (50.5 g) was frac-
H
2
3
a
3
tionated via silica gel CC, eluting with CHCl
to afford ten fractions A
ꢀA10 on the basis of TLC analysis. Fraction
(34.2 g) was further passed through a D101 macroporous resin
column eluted with H O, H O–EtOH (9:1, v/v), H O–EtOH (7:3, v/
v), H O–EtOH (1:1, v/v) and H O–EtOH (3:7, v/v), respectively. The
O (1:1, v/v) EtOH fraction (4.0 g) was separated by silica gel col-
umn chromatography using CHCl O gradient mixtures
ꢀMeOHꢀH
(8:2:0.2–5:5:0.5) to afford seven fractions (B ). Fraction B
ꢀB
(1.3 g) was subjected to an ODS CC (50 CNꢀH O)
M, 10ꢀ50% CH
to afford ten subfractions. Subfraction 3 (150 mg) was separated
by reversed-phase HPLC with 28% CH O containing 0.05%
CNꢀH
TFA (28:72, v/v) as mobile phase to yield compounds 1 (8 mg) and
(6 mg). Subfraction 5 (200 mg) was subjected to preparative HPLC
YMC-ODS-A 5
3
2
ꢀMeOHꢀH O (7:3:0.5),
D
a
D
1
D
-
A
5
a
2
2
2
1
6a
2
2
H
2
against five human cancer cell lines (HCT-8, Bel-7402, BGC-823,
A549, and A2780) with paclitaxel as a positive control. Compounds
3
2
1
7
5
obtained in this study were inactive (IC50 > 10
7
1
l
M) to HCT-8, Bel-
402, BGC-823, A549, and A2780 cell lines, except that compound
1 showed activity against all tested cell lines, with IC50 values
M.
l
3
2
3
2
ranging from 0.1 to 2.41
l
4
(
CH
l
M, 250 mm ꢁ 20 mm, detection at 210 nm) using
3
. Concluding remarks
3
CNꢀH
2
O containing 0.05% TFA (3:7, v/v, 7 mL/min) as mobile
phase to yield compounds 2 (10 mg), 5 (12 mg), and 6 (15 mg). Sub-
Based on the cytotoxic activity shown by the n-BuOH part of
5% EtOH extract of the stems of G. kwangsiensis, as a result, 11
fraction 6 (80 mg) was subjected to preparative HPLC (YMC-ODS-A
9
5
l
M, 250 mm ꢁ 20 mm, detection at 210 nm) using CH
containing 0.05% TFA (31:69, v/v, 7 mL/min) as mobile phase to yield
compounds 3 (11 mg), 7 (14 mg), and 8 (12 mg). The EtOH–H O (7:3,
v/v) fraction (300 mg) was purified by preparative HPLC (YMC-ODS-
2
A 5 O
3 2
CNꢀH O
new compounds were isolated and identified from n-BuOH part
of G. kwangsiensis. All of the isolated triterpenoid glycosides pos-
sessed an olean-12-ene skeleton and oligosaccharidic chains were
made up of four monosaccharide units linked to C-3. These com-
pounds were devoide of cytotoxicity except for compound 11.
2
l
M, 250 mm ꢁ 20 mm, detection at 210 nm) using CH
3
CNꢀH
containing 0.05% TFA (36:64, v/v, 7 mL/min) as mobile phase to yield
compounds 9 (25 mg), 10 (20 mg), and 11 (13 mg).
4
. Experimental
4.4. Acid hydrolysis and sugar analysis
4.1. General experimental procedures
The absolute configuration of the sugars in compounds 1–11
were determined as described previously (Fu et al., 2008, 2011).
Optical rotations were measured on a Perkin-Elmer 241 auto-
matic digital polarimeter. UV spectra were recorded using a Shima-
dzu UV-300 spectrophotometer. IR spectra were recorded on a
Nicolet 5700 FT-IR spectrometer by a transmission microscope
method. 1D and 2D NMR spectra were obtained at 500 and
4
.5. Cytotoxicity assay
Compounds 1–11 were tested for cytotoxicity against HCT-8
human colon cancer cell line), Bel-7402 (human hepatoma cancer
cell line), BGC-823 (human gastric cancer cell line), A549 (human
lung cancer cell line), and A2780 (human ovarian cancer cell line)
by means of the MTT method as described previously (Li et al.,
1
13
1
25 MHz for H and C, respectively, on an INOVA 500 MHz spec-
(
trometer in pyridine-d with solvent peaks as references. ESIMS
5
was obtained using an Agilent 1100 series LC/MSD Trap SL mass
spectrometer. HRESIMS was determined by an Agilent 6520 Accu-
rate-Mass Q-TOF LC/MS spectrometer. GC was conducted using an
Agilent Technologies 7890A instrument (Agilent). Preparative HPLC
was carried on a Shimadazu LC-6AD instrument with a SPD-20A
2
008).
4
.6. Gordonsaponin A (1)
detector, using a YMC-Pack ODS-A column (250 ꢁ 20 mm, 5
Column chromatography (CC) was performed with silica gel
200–300 mesh, Qingdao Marine Chemical Inc., Qingdao, People’s
Republic of China) and ODS (50 M, YMC, Japan). TLC was carried
lM).
20
D
White, amorphous powder; ½
a
ꢂ
ꢀ8.0 (c 0.09, MeOH); UV
(
(
1
MeOH) kmax (log
e
) 206 (3.87), 251 (3.39) nm; IR
672, 1430, 1373, 1199, 1137, 1078, 1045 cm ; h
m
max 3360, 2941,
l
ꢀ1
1
m
H NMR (pyri-
out with glass precoated silica gel GF254 plates. Spots were visual-
ized under UV light or by spraying with 10% sulfuric acid in EtOH
followed by heating.
13
dine-d
5 5
, 500 MHz) and C NMR (pyridine-d , 125 MHz) spectro-
+
scopic data, see Table 1; (+)-ESIMS m/z 1113 [M + Na] ; (ꢀ)-ESIMS
ꢀ
+
m/z 1089 [M ꢀ H] ; HRESIMS m/z 1113.5473 [M + Na] (calcd. for
23Na, 1113.5452).
53 86
C H O
4
.2. Plant material
4.7. Gordonsaponin B (2)
Stems of G. kwangsiensis were collected at Xishuangbanna, Yun-
2
D
0
nan Province, China, in May 2010 and identified by Prof. Jingyun
Cui (Xishuangbanna Tropical Botanical Garden, Chinese Academy
of Sciences). A voucher specimen (No. 21798) was deposited at
the Institute of Materia Medica, Chinese Academy of Medical Sci-
ences, Beijing 100050.
White, amorphous powder; ½
aꢂ
ꢀ5.2 (c 0.09, MeOH); UV
(
1
MeOH) kmax (loge) 206 (4.07), 254 (3.57) nm; IR mmax 3380, 2946,
673, 1431, 1373, 1201, 1139, 1080, 1046 cm ; h
, 500 MHz) and C NMR (pyridine-d
scopic data, see Table 1; (+)-ESIMS m/z 1129 [M + Na] ; (+)-ESIMS
m/z 1105 [M + H] ; HRESIMS m/z 1129.5423 [M + Na] (calcd. for
C H O24Na, 1129.5401).
53 86
ꢀ1
1
m
H NMR (pyri-
1
3
dine-d
5
5
, 125 MHz) spectro-
+
+
+
4.3. Extraction and isolation
Air-dried stems of G. kwangsiensis (9.80 kg) were extracted with
4.8. Gordonsaponin C (3)
9
5% EtOH (3 ꢁ 30 L) at reflux for 3 ꢁ 3 h, and the extract was evap-
orated under reduced pressure to yield a dark brown residue
220.2 g). The latter was suspended in H O (2000 mL) and then
2
D
0
White, amorphous powder; ½
aꢂ
ꢀ2.2 (c 0.08, MeOH); UV
(
2
(MeOH) kmax (loge) 206 (4.10) nm; IR mmax 3378, 2926, 1681,

1
72
H.-Z. Fu et al. / Phytochemistry 85 (2013) 167–174
1
458, 1378, 1246, 1201, 1142, 1077, 1043 cmꢀ1; 1H NMR (pyri-
dine-d , 500 MHz): Aglycone d 0.73 (1H, m, H-5), 0.82 (3H, s, H-
5), 1.01 (3H, s, H-26), 1.05 (3H, s, H-29), 1.06 (3H, s, H-24), 1.19
3H, s, H-23), 1.27 (3H, s, H-30), 1.38 (1H, m, H-19b), 1.70 (1H, m,
H-9), 1.81 (1H, m, H-11), 1.86 (3H, s, H-27), 2.04 (1H, m, H-21b),
70.1 (C-4), 73.7 (C-2), 75.0 (C-3), 76.3 (C-5), 103.2 (C-1); (+)-ESIMS
+
ꢀ
5
m/z 1113 [M + Na] ; (-)-ESIMS m/z 1089 [M ꢀ H] ; HRESIMS m/z
+
2
(
86
1113.5466 [M + Na] (calcd. for C53H O23Na, 1113.5452).
4.10. Gordonsaponin E (5)
2
3
3
4
.78 (1H, t, J = 12.0 Hz, H-21a), 2.86 (1H, t, J = 14.5 Hz, H-19a),
.02 (1H, br d, J = 14.5 Hz, H-18), 3.22 (1H, br d, J = 11.0 Hz, H-3),
.62 (1H, d, J = 10.5 Hz, H-28b), 3.78 (1H, d, J = 10.5 Hz, H-28a),
2
D
0
White, amorphous powder; ½
(MeOH) kmax (log ) 206 (4.12), 252 (3.62) nm; IR
2945, 1672, 1431, 1374, 1201, 1139, 1080, 1047 cm ; 1H NMR
(pyridine-d , 500 MHz): Aglycone d 0.76 (1H, m, H-5), 0.80 (3H, s,
a
ꢂ
ꢀ6.4 (c 0.05, MeOH); UV
e
m
max 3392,
ꢀ1
.25 (1H, m, H-15), 4.54 (1H, m, H-16), 5.46 (1H, br s, H-12), 6.19
0
(
1H, dd, J = 5.0/12.0 Hz, H-22); Ang d 1.82 (1H, s, H-5 ), 2.02 (1H,
5
0
0
q, J = 7.0 Hz, H-4 ), 5.83 (1H, q, J = 7.0 Hz, H-3 ); Sugars: GlcA d
.45 (1H, m, H-3), 4.48 (1H, m, H-4), 4.52 (1H, m, H-5), 4.65 (1H,
H-25), 1.03 (6H, s, H-26, H-29), 1.09 (3H, s, H-30), 1.11 (3H, s, H-
24), 1.25 (3H, s, H-23), 1.31 (1H, m, H-19b), 1.80 (3H, s, H-27),
1.68 (1H, m, H-9), 1.81 (1H, m, H-21b), 1.83 (1H, m, H-11), 2.06
(1H, m, H-21a), 2.25 (1H, m, H-22), 2.43 (1H, m, H-18), 2.68 (1H,
m, H-19a), 3.25 (1H, dd, J = 3.5/11.5 Hz, H-3), 3.59 (1H, d,
J = 10.5 Hz, H-28b), 3.78 (1H, d, J = 10.5 Hz, H-28a), 4.46 (1H, m,
H-15), 4.53 (1H, m, H-16), 5.42 (1H, br s, H-12); Sugars: GlcA d
4.41 (1H, m, H-3), 4.48 (1H, m, H-5), 4.50 (1H, m, H-4), 4.64 (1H,
t, J = 9.0 Hz, H-2), 4.87 (1H, d, J = 7.0 Hz, H-1), Xyl d 3.41 (1H, t,
J = 11.0 Hz, H-5b), 4.06 (1H, t, J = 8.0 Hz, H-3), 4.25 (1H, m, H-4),
4.31 (1H, m, H-5a), 4.53 (1H, dd, J = 6.5/8.5 Hz, H-2), 5.68 (1H, d,
J = 6.5 Hz, H-1), Glc d 4.00 (1H, t, J = 8.5 Hz, H-3), 4.22 (1H, dd,
J = 7.5/8.5 Hz, H-2), 4.32 (1H, m, H-6), 4.38 (1H, m, H-5), 4.50
(1H, m, H-4), 5.07 (1H, d, J = 7.5 Hz, H-1), Gal d 4.36 (1H, m, H-5),
4.42 (1H, m, H-6), 4.46 (1H, m, H-4), 4.47 (1H, m, H-2), 4.48 (1H,
m, H-3), 5.85 (1H, d, J = 7.5 Hz, H-1); Aglycone d 15.8 (C-25), 16.8
(C-24), 17.5 (C-26), 18.7 (C-6), 20.9 (C-27), 23.9 (C-11), 24.5 (C-
30), 26.5 (C-2), 28.0 (C-23), 31.0 (C-22), 31.2 (C-20), 33.4 (C-7),
33.4 (C-29), 36.7 (C-10), 36.9 (C-21), 38.7 (C-1), 38.9 (C-8), 39.5
(C-4), 41.0 (C-18), 43.2 (C-17), 47.2 (C-9), 47.8 (C-19), 47.9 (C-
14), 55.5 (C-5), 67.5 (C-15), 78.3 (C-16), 69.4 (C-28), 89.5 (C-3),
123.1 (C-12), 145.9 (C-13); Sugars: GlcA d 71.0 (C-4), 76.3 (C-5),
78.6 (C-2), 84.9 (C-3), 105.5 (C-1), 172.0 (C-6), Xyl d 67.3 (C-5),
70.8 (C-4), 77.1 (C-3), 83.7 (C-2), 101.8 (C-1), Glc d 61.7 (C-6),
4
t, J = 8.5 Hz, H-2), 4.83 (1H, d, J = 6.5 Hz, H-1), Xyl d 3.41 (1H, t,
J = 11.0 Hz, H-5b), 4.25 (1H, t, J = 8.0 Hz, H-3), 4.31 (1H, m, H-5a),
4
4
4
4
.47 (1H, m, H-4), 4.51 (1H, m, H-2), 5.74 (1H, br s, H-1), Glc d
.01 (1H, t, J = 8.5 Hz, H-3), 4.31 (1H, m, H-5), 4.32 (1H, m, H-2),
.36 (1H, m, H-6), 4.53 (1H, m, H-4), 5.02 (1H, br s, H-1), Glc d
0
.09 (1H, t, J = 9.0 Hz, H-3), 4.10 (1H, dd, J = 8.0/9.0 Hz, H-2), 4.33
(
1H, m, H-6b), 4.45 (1H, m, H-6a), 4.46 (1H, m, H-5), 4.47 (1H, m,
H-4), 6.00 (1H, d, J = 7.0 Hz, H-1); Aglycone d 15.8 (C-25), 16.7
C-24), 17.5 (C-26), 18.7 (C-6), 21.3 (C-27), 23.9 (C-11), 25.1 (C-
(
3
3
0), 26.6 (C-2), 27.8 (C-23), 32.0 (C-20), 32.5 (C-7), 33.4 (C-29),
6.7 (C-10), 38.9 (C-1), 39.5 (C-8), 39.5 (C-4), 41.4 (C-18), 41.7
(
C-21), 45.2 (C-17), 47.0 (C-9), 47.1 (C-14), 47.7 (C-19), 55.4 (C-
5
1
), 63.6 (C-28), 67.5 (C-15), 72.8 (C-22), 75.0 (C-16), 89.4 (C-3),
0
0
23.1 (C-12), 144.4 (C-13); Ang d 15.8 (C-4 ), 20.8 (C-5 ), 129.3
0
0
0
(
(
(
C-2 ), 136.4 (C-3 ), 167.9 (C-1 ); Sugars: GlcA d 71.1 (C-4), 76.9
C-5), 78.7 (C-2), 84.5 (C-3), 105.5 (C-1), 172.5 (C-6), Xyl d 67.6
C-5), 70.5 (C-4), 76.4 (C-3), 83.7 (C-2), 101.8 (C-1), Glc d 61.7 (C-
0
6
6
1
), 69.8 (C-4), 75.0 (C-2), 75.9 (C-5), 78.2 (C-3), 107.6 (C-1), Glc d
2.9 (C-6), 72.7 (C-2), 77.1 (C-4), 77.2 (C-3), 78.4 (C-5), 102.4 (C-
+
+
); (+)-ESIMS m/z 1227 [M + Na] ; (+)-ESIMS m/z 1205 [M + H] ;
+
HRESIMS m/z 1227.5816 [M + Na] (calcd. for
227.5823).
58 92
C H O26Na,
1
7
0.1 (C-4), 75.1 (C-2), 76.3 (C-5), 78.9 (C-3), 107.5 (C-1), Gal d
4
.9. Gordonsaponin D (4)
62.0 (C-6), 69.5 (C-4), 73.5 (C-2), 74.8 (C-3), 76.1 (C-5), 103.2 (C-
+
1
); (+)-ESIMS m/z 1105 [M + H] ; HRESIMS m/z 1129.5411
2
D
0
+
White, amorphous powder; ½
a
ꢂ
ꢀ3.6 (c 0.12, MeOH); UV
[M + Na] (calcd. for C53
86
H O24Na, 1129.5401).
(
2
(
MeOH) kmax (loge) 206 (3.92), 253 (3.77) nm; IR mmax 3345,
931, 1672, 1457, 1387, 1201, 1140, 1078, 1046 cm ; 1H NMR
, 500 MHz): Aglycone d 0.73 (1H, m, H-5), 0.80 (3H, s,
H-25), 0.89 (3H, s, H-26), 1.02 (3H, s, H-29), 1.10 (6H, s, H-23, H-
ꢀ1
4.11. Gordonsaponin F (6)
pyridine-d
5
2
D
0
White, amorphous powder; ½
(MeOH) kmax (log ) 206 (3.84), 253 (3.65) nm; IR
2975, 1658, 1530, 1438, 1179, 1152, 1080, 1046 cm ; 1H NMR
(pyridine-d , 500 MHz): Aglycone d 0.65 (1H, m, H-5), 0.73 (3H, s,
a
ꢂ
ꢀ8.6 (c 0.14, MeOH); UV
2
1
4), 1.27 (3H, s, H-30), 1.28 (1H, m, H-19b), 1.40 (1H, m, H-21),
.68 (1H, m, H-9), 1.80 (3H, s, H-27), 1.82 (1H, m, H-11), 2.18
e
m
max 3361,
ꢀ1
(
1H, m, H-15), 2.24 (1H, m, H-22), 2.46 (1H, br d, J = 13.5 Hz, H-
5
1
3
4
8), 2.70 (1H, t, J = 13.5 Hz, H-19a), 3.24 (1H, dd, J = 13.0 Hz, H-3),
.58 (1H, d, J = 10.5 Hz, H-28b), 3.70 (1H, d, J = 10.5 Hz, H-28a),
.60 (1H, m, H-16), 5.33 (1H, br s, H-12); Sugars: GlcA d 4.42 (1H,
H-25), 1.00 (3H, s, H-29), 1.06 (3H, s, H-30), 1.08 (3H, s, H-24),
1.25 (3H, s, H-23), 1.22 (1H, m, H-19b), 1.45 (3H, s, H-27), 1.48
(3H, s, H-26), 1.56 (1H, m, H-9), 1.80 (1H, m, H-11), 1.80 (1H, m,
H-21b), 2.05 (1H, m, H-21a), 2.14 (1H, m, H-18), 2.21 (1H, m, H-
15), 2.43 (1H, m, H-19a), 3.22 (1H, br d, J = 11.5 Hz, H-3), 3.61
(1H, d, J = 11.0 Hz, H-28b), 4.00 (1H, d, J = 11.0 Hz, H-28a), 4.51
(1H, m, H-16), 4.53 (1H, m, H-22), 5.31 (1H, br s, H-12); Sugars:
GlcA d 4.48 (1H, m, H-3), 4.48 (1H, m, H-4), 4.49 (1H, m, H-5),
4.65 (1H, t, J = 8.5 Hz, H-2), 4.82 (1H, d, J = 7.5 Hz, H-1), Xyl d
3.77 (1H, t, J = 10.5 Hz, H-5b), 4.05 (1H, t, J = 8.0 Hz, H-3), 4.28
(1H, m, H-4), 4.31 (1H, m, H-5a), 4.48 (1H, m, H-2), 5.71 (1H, d,
J = 7.5 Hz, H-1), Glc d 4.00 (1H, t, J = 8.5 Hz, H-3), 4.22 (1H, m, H-
5), 4.23 (1H, dd, J = 8.0/8.5 Hz, H-2), 4.23 (1H, m, H-4), 4.36 (1H,
m, H-6), 5.04 (1H, d, J = 8.0 Hz, H-1), Gal d 4.35 (1H, m, H-5), 4.44
(1H, m, H-4), 4.44 (1H, m, H-6), 4.48 (1H, m, H-2), 4.49 (1H, m,
H-3), 5.85 (1H, d, J = 7.5 Hz, H-1); 22-OAc d 2.11 (3H, s); Aglycone
d 15.3 (C-25), 16.4 (C-24), 18.0 (C-26), 18.0 (C-6), 23.4 (C-11), 25.0
(C-30), 26.6 (C-27), 26.8 (C-2), 27.6 (C-23), 30.8 (C-7), 31.2 (C-20),
32.6 (C-15), 33.5 (C-29), 36.4 (C-10), 38.4 (C-1), 39.7 (C-8), 39.3 (C-
4), 41.4 (C-18), 41.4 (C-14), 43.6 (C-17), 44.1 (C-21), 46.5 (C-9),
47.1 (C-19), 55.3 (C-5), 68.7 (C-28), 69.8 (C-16), 72.2 (C-22), 89.3
m, H-3), 4.47 (1H, m, H-4), 4.47 (1H, m, H-5), 4.64 (1H, t,
J = 8.5 Hz, H-2), 4.87 (1H, d, J = 7.5 Hz, H-1), Xyl d 3.41 (1H, t,
J = 12.0 Hz, H-5b), 4.08 (1H, t, J = 8.0 Hz, H-3), 4.25 (1H, m, H-4),
4
.31 (1H, m, H-5a), 4.49 (1H, dd, J = 7.5/8.5 Hz, H-2), 5.68 (1H, d,
J = 7.5 Hz, H-1), Glc d 4.00 (1H, t, J = 8.5 Hz, H-3), 4.22 (1H, dd,
J = 7.5/8.5 Hz, H-2), 4.32 (1H, m, H-6), 4.34 (1H, m, H-5), 4.47
(
1H, m, H-4), 5.06 (1H, d, J = 7.5 Hz, H-1), Gal d 4.36 (1H, m, H-5),
.42 (1H, m, H-6), 4.48 (1H, m, H-3), 4.49 (1H, m, H-2), 4.52 (1H,
m, H-4), 5.85 (1H, d, J = 7.5 Hz, H-1); Aglycone d 15.6 (C-25), 16.7
C-24), 16.9 (C-26), 18.4 (C-6), 23.7 (C-11), 24.7 (C-23), 26.3 (C-
4
(
2
3
), 27.3 (C-27), 28.0 (C-30), 30.5 (C-22), 31.3 (C-20), 33.1 (C-29),
3.4 (C-7), 34.7 (C-15), 36.7 (C-10), 37.1 (C-21), 38.7 (C-1), 39.5
(
4
C-4), 39.9 (C-8), 40.9 (C-17), 41.9 (C-18), 42.4 (C-14), 46.9 (C-9),
8.3 (C-19), 55.7 (C-5), 69.6 (C-28), 74.2 (C-16), 89.5 (C-3), 123.1
(C-12), 145.1 (C-13); Sugars: GlcA d 71.1 (C-4), 76.9 (C-5), 78.9
(C-2), 84.7 (C-3), 105.5 (C-1), 172.0 (C-6), Xyl d 67.5 (C-5), 70.6
(C-4), 77.1 (C-3), 83.5 (C-2), 101.7 (C-1), Glc d 61.6 (C-6), 70.1 (C-
4
), 75.0 (C-2), 76.0 (C-5), 78.2 (C-3), 107.4 (C-1), Gal d 61.9 (C-6),

H.-Z. Fu et al. / Phytochemistry 85 (2013) 167–174
173
(
5
7
(
6
2
C-3), 125.3 (C-12), 142.1 (C-13); Sugars: GlcA d 71.6 (C-4), 76.8 (C-
), 78.6 (C-2), 84.3 (C-3), 105.3 (C-1), 171.8 (C-6), Xyl d 67.2 (C-5),
0.8 (C-4), 76.9 (C-3), 83.3 (C-2), 101.5 (C-1), Glc d 61.5 (C-6), 70.4
(1H, m, H-6), 4.51 (1H, m, H-4), 5.09 (1H, d, J = 6.0 Hz, H-1), Gal d
4.35 (1H, m, H-5), 4.44 (1H, m, H-6), 4.47 (1H, m, H-3), 4.47 (1H,
m, H-4), 4.49 (1H, m, H-2), 5.86 (1H, d, J = 7.5 Hz, H-1); Aglycone
d 15.8 (C-25), 16.8 (C-24), 17.5 (C-26), 18.8 (C-6), 21.3 (C-27),
23.9 (C-11), 25.1 (C-30), 26.6 (C-2), 28.0 (C-23), 32.0 (C-20), 33.4
(C-29), 36.7 (C-7), 36.7 (C-10), 38.9 (C-1), 39.5 (C-4), 39.5 (C-8),
41.4 (C-18), 41.7 (C-21), 45.2 (C-17), 47.0 (C-9), 47.1 (C-14), 47.7
C-4), 74.8 (C-2), 75.8 (C-5), 78.0 (C-3), 107.2 (C-1), Gal d 61.8 (C-6),
9.4 (C-4), 73.5 (C-2), 74.8 (C-3), 76.1 (C-5), 102.9 (C-1), 22-OAc d
+
1.8 (C-2), 169.7 (C-1); (+)-ESIMS m/z 1171 [M + Na] ; HRESIMS m/
+
z 1171.5520 [M + Na] (calcd. for C55
H
88
O
25Na, 1171.5507).
(
C-19), 55.5 (C-5), 62.9 (C-28), 67.4 (C-15), 72.7 (C-22), 75.0 (C-
0
4.12. Gordonsaponin G (7)
16), 89.4 (C-3), 123.1 (C-12), 144.4 (C-13); Ang d 15.8 (C-4 ), 20.8
(
0
0
0
0
C-5 ), 129.3 (C-2 ), 136.4 (C-3 ), 167.9 (C-1 ); Sugars: GlcA d 71.0
2
D
0
White, amorphous powder; ½
aꢂ
ꢀ2.9 (c 0.10, MeOH); UV
(C-4), 76.9 (C-5), 79.0 (C-2), 84.8 (C-3), 105.2 (C-1), 172.1 (C-6),
Xyl d 67.5 (C-5), 70.7 (C-4), 77.1 (C-3), 83.4 (C-2), 101.9 (C-1), Glc
d 61.7 (C-6), 70.2 (C-4), 75.0 (C-2), 76.3 (C-5), 78.3 (C-3), 107.4
(C-1), Gal d 62.0 (C-6), 69.8 (C-4), 73.8 (C-2), 75.1 (C-3), 76.2 (C-
(
1
MeOH) kmax (loge) 206 (3.80) nm; IR mmax 3395, 2928, 1728,
ꢀ1
1
679, 1433, 1376, 1203, 1142, 1079, 1046 cm
, 500 MHz): Aglycone d 0.72 (1H, m, H-5), 0.77 (3H, s, H-
5), 0.85 (3H, s, H-26), 1.04 (3H, s, H-29), 1.12 (3H, s, H-24), 1.28
6H, s, H-23, H-30), 1.31 (1H, m, H-19b), 1.70 (1H, m, H-9), 1.84
1H, m, H-11), 1.87 (3H, s, H-27), 2.04 (1H, m, H-21b), 2.31 (1H,
; H NMR (pyri-
dine-d
5
+
2
(
(
5), 103.2 (C-1); (+)-ESIMS m/z 1227 [M + Na] ; (ꢀ)-ESIMS m/z
ꢀ
+
1203 [M ꢀ H] ; HRESIMS m/z 1227.5795 [M + Na] (calcd. for
58 92
C H O26 Na, 1227.5823).
m, H-15), 2.82 (1H, m, H-21a), 2.89 (1H, t, J = 13.5 Hz, H-19a),
3
3
4
1
4
4
.04 (1H, br d, J = 13.5 Hz, H-18), 3.25 (1H, br d, J = 11.5 Hz, H-3),
.42 (1H, d, J = 10.5 Hz, H-28b), 4.36 (1H, d, J = 10.5 Hz, H-28a),
.64 (1H, m, H-16), 5.38 (1H, br s, H-12), 6.21 (1H, dd, J = 5.5/
4
.14. Gordonsaponin I (9)
20
D
White, amorphous powder; ½
a
ꢂ
ꢀ13.8 (c 0.13, MeOH); UV
max 3359,
0
1.5 Hz, H-22); Ang d 1.94 (1H, s, H-5 ), 2.09 (1H, q, J = 6.5 Hz, H-
(
MeOH) kmax (log
e
) 206 (4.04), 251 (3.71) nm; IR
m
0
0
), 5.87 (1H, q, J = 6.5 Hz, H-3 ); Sugars: GlcA d 4.47 (1H, m, H-3),
.48 (1H, m, H-4), 4.49 (1H, m, H-5), 4.66 (1H, m, H-2), 4.86 (1H,
947, 1676, 1432, 1375, 1202, 1139, 1080, 1047 cm ; 1H NMR
ꢀ
1
2
1
3
(
pyridine-d
5 5
, 500 MHz) and C NMR (pyridine-d , 125 MHz) are
br s, H-1), Xyl d 3.42 (1H, t, J = 10.5 Hz, H-5b), 4.08 (1H, t,
J = 8.5 Hz, H-3), 4.36 (1H, m, H-4), 4.36 (1H, m, H-5a), 4.52 (1H,
dd, J = 7.0/8.5 Hz, H-2), 5.72 (1H, d, J = 7.0 Hz, H-1), Glc d 4.02
+
given in Table 1; (+)-ESIMS m/z 1285 [M + Na] ; (ꢀ)-ESIMS m/z
ꢀ
+
1
H O
94
261 [M ꢀ H] ; HRESIMS m/z 1285.5797 [M + Na] (calcd. for C60-
28Na, 1285.5824).
(
1H, t, J = 8.5 Hz, H-3), 4.25 (1H, dd, J = 7.5/8.5 Hz, H-2), 4.25 (1H,
m, H-5), 4.27 (1H, m, H-4), 4.36 (1H, m, H-6), 5.08 (1H, d,
J = 7.5 Hz, H-1), Gal d 4.37 (1H, m, H-5), 4.45 (1H, m, H-6), 4.47
4.15. Gordonsaponin J (10)
(
1H, m, H-3), 4.51 (1H, m, H-2), 4.53 (1H, m, H-4), 5.87 (1H, d,
J = 6.5 Hz, H-1); Aglycone d 15.6 (C-25), 16.7 (C-24), 16.8 (C-26),
8.4 (C-6), 23.8 (C-11), 25.2 (C-30), 26.5 (C-2), 27.6 (C-27), 28.0
C-23), 32.1 (C-20), 33.1 (C-7), 33.5 (C-29), 35.1 (C-15), 36.7 (C-
2
D
0
White, amorphous powder; ½
a
ꢂ
ꢀ24.8 (c 0.05, MeOH); UV
max 2975, 1655, 1531,
1H NMR (pyridine-d
1
(
(MeOH) kmax (loge) 204 (4.08) nm; IR m
1438, 1179, 1152, 1131, 1015 cm
ꢀ1
;
5
,
1
4
0), 38.7 (C-1), 39.6 (C-4), 40.1 (C-8), 40.9 (C-18), 41.6 (C-14),
1.7 (C-21), 44.8 (C-17), 46.9 (C-9), 47.4 (C-19), 55.7 (C-5), 63.6
500 MHz): Aglycone d 0.74 (3H, s, H-25), 0.78 (1H, m, H-5), 0.94
(3H, s, H-26), 1.05 (3H, s, H-29), 1.13 (3H, s, H-24), 1.25 (6H, s, H-
23, H-30), 1.47 (1H, m, H-19b), 1.74 (1H, m, H-9), 1.79 (3H, s, H-
27), 1.85 (1H, m, H-11), 2.37 (1H, m, H-18), 2.68 (1H, m, H-19a),
3.28 (1H, br d, J = 11.5 Hz, H-3), 3.53 (1H, d, J = 10.0 Hz, H-28b),
3.74 (1H, d, J = 10.0 Hz, H-28a), 4.38 (1H, m, H-15), 4.48 (1H, m,
H-16), 5.51 (1H, br s, H-12), 5.79 (1H, d, J = 10.5 Hz, H-21), 6.23
(
(
C-28), 70.1 (C-16), 89.5 (C-3), 73.0 (C-22), 123.1 (C-12), 143.7
C-13); Ang d 15.8 (C-4 ), 20.9 (C-5 ), 129.3 (C-2 ), 136.5 (C-3 ),
0
0
0
0
0
1
68.0 (C-1 ); Sugars: GlcA d 71.1 (C-4), 76.9 (C-5), 79.0 (C-2), 84.7
(
(
C-3), 105.5 (C-1), 172.5 (C-6), Xyl d 67.6 (C-5), 70.7 (C-4), 77.1
C-3), 83.7 (C-2), 101.8 (C-1), Glc d 61.7 (C-6), 70.2 (C-4), 75.0 (C-
0
2
7
1
1
), 76.0 (C-5), 78.3 (C-3), 107.3 (C-1), Gal d 62.0 (C-6), 69.8 (C-4),
3.8 (C-2), 75.1 (C-3), 76.3 (C-5), 103.2 (C-1); (+)-ESIMS m/z
(1H, d, J = 10.5 Hz, H-22); Ang d 2.00 (1H, s, H-5 ), 2.09 (1H, q,
0
0
J = 7.0 Hz, H-4 ), 5.86 (1H, q, J = 7.5 Hz, H-3 ); Sugars: GlcA d 4.38
(1H, m, H-3), 4.49 (1H, m, H-5), 4.50 (1H, m, H-4), 4.68 (1H, t,
J = 8.5 Hz, H-2), 4.87 (1H, d, J = 7.5 Hz, H-1), Xyl d 3.54 (1H, t,
J = 10.5 Hz, H-5b), 4.08 (1H, t, J = 8.5 Hz, H-3), 4.28 (1H, m, H-4),
4.38 (1H, m, H-5a), 4.50 (1H, m, H-2), 5.70 (1H, d, J = 8.0 Hz, H-1),
Glc d 4.00 (1H, t, J = 8.5 Hz, H-3), 4.23 (1H, m, H-5), 4.23 (1H, dd,
J = 7.5/8.5 Hz, H-2), 4.37 (1H, m, H-6), 4.48 (1H, m, H-4), 5.07
(1H, d, J = 7.5 Hz, H-1), Gal d 4.35 (1H, m, H-5), 4.44 (1H, m, H-6),
4.46 (1H, m, H-4), 4.47 (1H, m, H-3), 4.49 (1H, m, H-2), 5.86 (1H,
d, J = 7.5 Hz, H-1); 16-OAc d 2.44 (3H, s), 21-OAc d 2.01 (3H, s);
Aglycone d 15.7 (C-25), 16.7 (C-24), 17.5 (C-26), 18.7 (C-6), 19.5
(C-30), 21.7 (C-27), 23.9 (C-11), 26.6 (C-2), 28.0 (C-23), 29.4 (C-
29), 36.0 (C-7), 36.7 (C-10), 36.7 (C-20), 38.9 (C-1), 39.4 (C-8),
39.5 (C-4), 41.6 (C-18), 45.4 (C-17), 47.0 (C-14), 47.2 (C-19), 47.5
(C-9), 55.3 (C-5), 63.3 (C-28), 66.8 (C-15), 72.0 (C-22), 75.1 (C-
16), 78.3 (C-21), 89.4 (C-3), 126.4 (C-12), 142.3 (C-13); Ang d
+
ꢀ
187 [M + Na] ; (ꢀ)-ESIMS m/z 1211 [M ꢀ H] ; HRESIMS m/z
+
92
211.5805 [M + Na] (calcd. for C58H O25Na, 1211.5820).
4.13. Gordonsaponin H (8)
2
D
m
0
White, amorphous powder; ½
a
ꢂ
ꢀ0.5 (c 0.13, MeOH); UV
(
1
5
MeOH) kmax (log
e
) 206 (3.64); IR
max 3396, 2933, 1679, 1432,
377, 1201, 1141, 1079, 1045 cmꢀ1;
1
5
H NMR (pyridine-d ,
00 MHz): Aglycone d 0.78 (1H, m, H-5), 0.81 (3H, s, H-25), 1.00
(
3H, s, H-26), 1.04 (3H, s, H-29), 1.08 (3H, s, H-24), 1.27 (6H, s, H-
23, H-30), 1.30 (1H, m, H-19b), 1.69 (1H, m, H-9), 1.78 (1H, m, H-
11), 1.85 (3H, s, H-27), 2.04 (1H, m, H-21b), 2.79 (1H, m, H-21a),
2.86 (1H, t, J = 13.0 Hz, H-19a), 3.01 (1H, br d, J = 13.5 Hz, H-18),
3.24 (1H, br d, J = 11.5 Hz, H-3), 3.62 (1H, d, J = 10.0 Hz, H-28b),
3.76 (1H, d, J = 10.0 Hz, H-28a), 4.33 (1H, m, H-15), 4.53 (1H, m,
0
0
0
0
0
H-16), 5.48 (1H, br s, H-12), 6.18 (1H, dd, J = 5.5/11.5 Hz, H-22);
Ang d 1.82 (1H, s, H-5 ), 2.02 (1H, q, J = 7.0 Hz, H-4 ), 5.83 (1H, q,
J = 7.0 Hz, H-3 ); Sugars: GlcA d 4.47 (1H, m, H-5), 4.50 (1H, m, H-
15.8 (C-4 ), 20.9 (C-5 ), 129.0 (C-2 ), 137.7 (C-3 ), 167.5 (C-1 ); Sug-
ars: GlcA d 71.0 (C-4), 77.0 (C-5), 78.9 (C-2), 84.5 (C-3), 105.5 (C-1),
172.0 (C-6), Xyl d 67.8 (C-5), 70.7 (C-4), 77.2 (C-3), 83.6 (C-2), 101.8
(C-1), Glc d 61.7 (C-6), 70.2 (C-4), 75.1 (C-2), 76.1 (C-5), 79.2 (C-3),
107.5 (C-1), Gal d 62.0 (C-6), 69.7 (C-4), 73.8 (C-2), 76.3 (C-3), 78.3
(C-5), 103.2 (C-1), 16-OAc d 21.9 (C-2), 170.8 (C-1), 21-OAc d 20.7
0
0
0
3
), 4.51 (1H, m, H-4), 4.66 (1H, t, J = 8.0 Hz, H-2), 4.86 (1H, d,
J = 5.5 Hz, H-1), Xyl d 3.42 (1H, t, J = 10.0 Hz, H-5b), 4.07 (1H, t,
J = 8.0 Hz, H-3), 4.26 (1H, m, H-5a), 4.28 (1H, m, H-4), 4.50 (1H,
m, H-2), 5.68 (1H, d, J = 6.0 Hz, H-1), Glc d 4.00 (1H, t, J = 8.5 Hz,
H-3), 4.23 (1H, dd, J = 6.0/8.5 Hz, H-2), 4.24 (1H, m, H-5), 4.34
+
(C-2), 170.3 (C-1); (+)-ESIMS m/z 1327 [M + Na] ; HRESIMS m/z
1327.5945 [M + Na] (calcd. for C62
+
96
H O
29Na, 1327.5929).

1
74
H.-Z. Fu et al. / Phytochemistry 85 (2013) 167–174
Athukoralage, P.S., Herath, H.M.T.B., Deraniyagala, S.A., Wijesundera, R.L.C.,
4
.16. Gordonsaponin K (11)
Weerasinghe, P.A., 2001. Antifungal constituent from Gordonia dassanayakei.
Fitoterapia 72, 565–567.
Botany Editorial Board, the Chinese Academy of Sciences., 1998. Flora of China.
Science Press, Beijing, p. 211.
2
D
0
White, amorphous powder; ½
a
ꢂ
ꢀ9.0 (c 0.08, MeOH); UV
(
MeOH) kmax (loge) 206 (4.02) nm; IR mmax 3400, 2928, 1679,
ꢀ
1
1
Fu, J., Yang, J.Z., Chen, R.Y., Zhang, D.M., 2008. Oligosaccharide polyester and
triterpenoid saponins from the roots of Polygala japonica. Phytochemistry 69,
1
d
443, 1374, 1205, 1144, 1079, 1047 cm ; h
m
H NMR (pyridine-
1
3
5
, 500 MHz) and C NMR (pyridine-d
5
, 125 MHz) spectroscopic
1617–1624.
+
data see Table 1; (+)-ESIMS m/z 1239 [M + Na] ; HRESIMS m/z
1
Fu, H.Z., Li, C.J., Yang, J.Z., Shen, Z.F., Zhang, D.M., 2011. Potential anti-inflammatory
+
constituents of the stems of Gordonia chrysandra. J. Nat. Prod. 74, 1066–1072.
92
239.5761 [M + Na] (calcd. for C59H O26Na, 1239.5769).
Acknowledgment
Herath, H.M.T.B., Athukoralage, P.S., 1998. Oleanane triterpenoids from Gordonia
ceylanica. Nat. Prod. Sci. 4, 253–256.
Herath, H.M.T.B., Athukoralage, P.S., 2000. Triterpenoids of Gordonia dassanayakei.
Nat. Prod. Sci. 6, 102–105.
Herath, H.M.T.B., Athukoralage, P.S., Jamie, J.F., 1999. Triterpenoids and steroids
from Gordonia dassanayakei. Communications 9, 3–8.
Herath, H.M.T.B., Athukoralage, P.S., Jamie, J.F., 2000. Two oleanane triterpenoids
from Gordonia ceylanica and their conversions to taraxarane triterpenoids.
Phytochemistry 54, 823–827.
Financial support was provided by the National Natural Science
Foundation of China (NSFC, Grant No. 21132009 and No.
2
0972191). The authors thank our colleagues of our institute: Pro-
fessor X.J. Jin for NMR measurements, Professor J.B. Li for MS mea-
surements, and Professors X.G. Chen and Z.F. Shen for bioassays.
Appendix A. Supplementary data
Herath, H.M.T.B., Athukoralage, P.S., Jamie, J.F., 2001. A new oleanane triterpenoid
from Gordonia ceylanica. Nat. Prod. Lett. 15, 339–344.
Li, C.J., Zhang, D.M., Luo, Y.M., Yu, S.S., Li, Y., Lu, Y., 2008. Bis-sesquiterpenes and
diterpenes from Chloranthus henryi. Phytochemistry 69, 2867–2874.
Lu, Y., Umeda, T., Yagi, A., Sakata, K., Chaudhuri, T., Ganguly, D.K., Sarma, S., 2000.
Triterpenoid saponins from the roots of tea plant (Camellia sinensis var.
assamica). Phytochemistry 53, 941–946.
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.phytochem.2012.
0
8.019.
Wang, C.C., Chen, L.G., Yang, L.L., 2001. Camelliin B induced apoptosis in HeLa cell
line. Toxicology 168, 231–240.
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