Two new furostanol saponins from Aspidistra typica

Article abstract of DOI:10.1080/10286020.2013.787991

Two new furostanol saponins (1 and 2), along with one known saponin (3), were obtained from the rhizomes of Aspidistra typica Baill. Their structures were elucidated as (25R)-26-O-β-D-glucopyranosyl-furost-5-ene-12-one- 3β,22α,26-triol-3-O-β-Dglucopyranosyl-(1 → 2)-[β-D-xylopyranosyl-(1 → 3)]-β-D-glucopyranosyl-(1 → 4)-β-D-galactopyranoside (1, typaspidoside A), (25S)-26-O-β-D- glucopyranosyl-furost-5-ene-12-one-3β,22α,26-triol-3-O-β-D- glucopyranosyl-(1 → 2)-[β-D-xylopyranosyl- (1 → 3)]-β-D-glucopyranosyl-(1 → 4)-β-D-galactopyranoside (2, 25S-typaspidoside A), and timosaponin H₁ (3), based on the integrative spectroscopic analysis of 1Dand 2D-NMR experiments, ESI-MS data and chemical evidence. The investigation on the chemical components of this plant is reported for the first time.

Full text of DOI:10.1080/10286020.2013.787991

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Two new furostanol saponins from
Aspidistra typica
Jiang-Ming Cui a b , Li-Ping Kang b c , He-Shui Yu b c , Yang Zhao b ,
Cheng-Qi Xiong b , Chao Liu b & Bai-Ping Ma b
a School of Pharmaceutical Sciences, Central South University ,
Changsha , 410013 , China
b Department of Biotechnology , Beijing Institute of Radiation
Medicine , Beijing , 100850 , China
c Graduate School of Tianjin University of Traditional Chinese
Medicine , Tianjin , 300193 , China
Published online: 16 May 2013.
To cite this article: Jiang-Ming Cui , Li-Ping Kang , He-Shui Yu , Yang Zhao , Cheng-Qi Xiong , Chao
Liu & Bai-Ping Ma (2013) Two new furostanol saponins from Aspidistra typica , Journal of Asian
Natural Products Research, 15:5, 525-531, DOI: 10.1080/10286020.2013.787991
To link to this article: http://dx.doi.org/10.1080/10286020.2013.787991
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Journal of Asian Natural Products Research, 2013
Vol. 15, No. 5, 525–531, http://dx.doi.org/10.1080/10286020.2013.787991
Two new furostanol saponins from Aspidistra typica
Jiang-Ming Cuiab, Li-Ping Kangbc, He-Shui Yubc, Yang Zhaob, Cheng-Qi Xiongb,
Chao Liub* and Bai-Ping Mab*
aSchool of Pharmaceutical Sciences, Central South University, Changsha 410013, China;
bDepartment of Biotechnology, Beijing Institute of Radiation Medicine, Beijing 100850, China;
cGraduate School of Tianjin University of Traditional Chinese Medicine, Tianjin 300193, China
(Received 27 December 2012; final version received 17 March 2013)
Two new furostanol saponins (1 and 2), along with one known saponin (3), were
obtained from the rhizomes of Aspidistra typica Baill. Their structures were elucidated
as (25R)-26-O-b-D-glucopyranosyl-furost-5-ene-12-one-3b,22a,26-triol-3-O-b-D-
glucopyranosyl-(1 ! 2)-[b-D-xylopyranosyl-(1 ! 3)]-b-D-glucopyranosyl-(1 ! 4)-
b-D-galactopyranoside (1, typaspidoside A), (25S)-26-O-b-D-glucopyranosyl-furost-5-
ene-12-one-3b,22a,26-triol-3-O-b-D-glucopyranosyl-(1 ! 2)-[b-D-xylopyranosyl-
(1 ! 3)]-b-D-glucopyranosyl-(1 ! 4)-b-D-galactopyranoside (2, 25S-typaspidoside
A), and timosaponin H1 (3), based on the integrative spectroscopic analysis of 1D-
and 2D-NMR experiments, ESI-MS data and chemical evidence. The investigation on
the chemical components of this plant is reported for the first time.
Keywords: Aspidistratypica;furostanolsaponins;typaspidosideA;25S-typaspidosideA
1. Introduction
were isolated from the dried rhizomes of A.
typica, and their structures were character-
ized by 1D-NMR (1H and 13C NMR), 2D-
NMR (correlated spectrometry (COSY),
HSQC, and heteronuclear multiple bond
coherence (HMBC)), MS data, and chemi-
cal evidence.
The family Convallariaceae, mainly con-
sisting of Speirantha, Convallaria, Ther-
opogon, Rohdea, Reineckia, Aspidistra, and
Tupistra, is known for its rich source of
steroidal saponins. To our best knowledge,
many steroidal saponins with the character-
ized skeleton of polyhydroxylated A/B ring
were reported from Convallariaceae [1].
Aspidistra typica Baill. is a perennial
herbaceous plant which belongs to the
genus Aspidistra with approximately 50
species [2]. It is being used to treat fractures,
congestion, and snakebite as a folk herbal
medicine. However, no more than 25
compounds were isolated from the genus
Aspidistra [3–12]. With a purpose of
searching for steroidal saponins with novel
structures and bioactivities, studies on the
constituents of A. typica were carried out. It
was described here that two new steroidal
saponins, along with one known compound,
2. Results and discussion
The ethanol extracts of A. typica were
extracted with n-BuOH to obtain the total
saponins. The n-BuOH fraction was
chromatographed on silica gel, MCI
CHP20/P50, and octadecylsilyl (ODS)
silica gel columns, and finally purified by
semi-preparative high performance liquid
chromatography (HPLC) to give three
compounds 1–3 (Figure 1). By comparing
the NMR and MS data with those in the
literature [13], compound 3 was deter-
mined as timosaponin H1.
*Corresponding authors. Email: liuchao9588@sina.com; mabaiping@sina.com
q 2013 Taylor & Francis

526
J.-M. Cui et al.
Glc3
HO
HO
HO
O
O
27
25
24
R2
OH
OH
26
23
21
20
17
R1 18
22
O
11
12
13
19
16
1
9
15
2
14
8
10
3
7
Glc1
HO
5
OH
O
O
OH
O
6
4
O
Xyl
O
O
O
HO
OH
HO
HO
OH
O
OH
HO
HO
Gal
OH
Glc2
R1
O
R2
eq-CH3
1
O
ax-CH3
2
3
H2 ax-CH3
Figure 1. The structures of compounds 1–3.
Compound 1 was isolated as a white
amorphous solid, which showed positive
color reaction in Liebermann–Burchard
and Ehrlich reagent tests, indicating a
furostanol saponin. Its molecular formula
C56H90O29 was deduced from the pseudo-
molecular ion peak at m/z 1225.5457 [M–
H]2 in the HR-ESI-MS, which was further
(d, J ¼ 7.8 Hz, H-1 of Xyl), and 5.57 (d,
J ¼ 7.8 Hz, H-1 of Glc2) were observed,
and the b-configuration of each sugar
residue was confirmed by the J1,2 value
1
(.7.0 Hz) in the H NMR spectrum [14].
Meanwhile, five anomeric carbon signals
at d 105.0 (C-1 of Glc3), 102.8 (C-1 of
Gal), 105.2 (C-1 of Glc1), 105.0 (C-1 of
Xyl), and 104.9 (C-1 of Glc2) were
assigned in the HSQC spectrum.
1
supported by the H and 13C NMR data.
The existence of four hexose units and
one pentose unit was proved by the
fragment ion peaks in the negative-ion
ESI-MS at m/z 1093 [M–H–132]2, 1063
[M–H–162]2, 931 [M–H–132–162]2,
751 [M–H–132–162–162–18]2, 589
[M–H–132–162–162–162–18]2, and
427 [M–H–132–162–162–162–18–
162]2. The sugar moieties consisting of
one D-galactose, three D-glucoses, and one
D-xylose were established by acid hydroly-
sis experiment. Five anomeric proton
signals at d 4.80 (d, J ¼ 7.8 Hz, H-1 of
Glc3), 4.86 (d, J ¼ 7.8 Hz, H-1 of Gal),
5.18 (d, J ¼ 8.4 Hz, H-1 of Glc1), 5.22
1
In the H NMR spectrum, two singlet
signals at d 1.14 (3H, s, CH3-18) and 0.89
(3H, s, CH3-19) and two doublet signals at
d 1.53 (3H, d, J ¼ 6.6 Hz, CH3-21) and
0.97 (3H, d, J ¼ 7.2 Hz, CH3-27) were
suggested to be characteristic steroidal
methyls. A series of typical carbon signals
at d 140.8, 121.4, 110.8, and 212.8
revealed the presence of D5(6), a-orien-
tation of 22-OH [15], and one ketonic
carbonyl group in the furostanol skeleton.
The ketonic carbonyl group at C-12 was
confirmed by the HMBC correlations
between C-12 at d 212.8 and Ha-11 at d

Journal of Asian Natural Products Research
527
O
HO
HO
O
OH
H
HO
OH
O
CH3
H3C
CH3
O
H
H
CH3
H
H
OH
O
O
O
HO
OH
O
O
O
O
H
HO
HO
HO
OH
OH
H
H
OH
O
HO
HO
OH
H
Figure 2. Key HMBC correlations for compound 1.
2.27, Hb-11 at d 2.51, H-18 at d 1.14, and
H-17 at d 2.93 (Figure 2). According to the
chemical shift difference between two
proton signals of C-26 (Dab ¼ 0.34), the
C-25 configuration was recognized as R
[16]. By comparing the NMR data with
those in the literature, aglycone of 1 was
positive Liebermann–Burchard and Ehr-
lich reactions. The HR-ESI-MS showed a
quasi-molecular ion peak at m/z 1225.5453
[M–H]2, corresponding to the molecular
formula C56H90O29. All the MS and NMR
data of 1 and 2 were closely similar, except
that the chemical shifts of two protons of C-
26 were slightly but distinctly different
between 1 and 2 in the 1H NMR spectrum.
The signals at d 4.07 (1H, 26-Ha) and 3.49
(1H, 26-Hb) of 2 were instead of the signals
at d 3.94 (1H, 26-Ha) and 3.60 (1H, 26-Hb)
of 1. So the C-25 configuration of 2 should
be S [16]. Accordingly, the structure of 2
was determined as (25S)-26-O-b-D-gluco-
pyranosyl-furost-5-en-12-one-3b,22a,26-
triol-3-O-b-D-glucopyranosyl-(1 ! 2)-[b-
D-xylopyranosyl-(1 ! 3)]-b-D-glucopyra-
nosyl-(1 ! 4)-b-D-galactopyranoside, an
epimer of 1, named 25S-typaspidoside A.
elucidated
as
(25R)-furost-5-ene-
3b,22a,26-triol-12-one [17,18].
Connections among sugars and the
sugar linkage sites to the aglycone were
validated by the HMBC correlations of H-1
of Glc3 at d 4.80 with C-26 at d 75.3, H-1 of
Xyl at d 5.22 with C-3 of Glc1 at d 86.8, H-1
of Glc2 at d 5.57 with C-2 of Glc1 at d 81.4,
H-1 of Glc1 at d 5.18 with C-4 of Gal at d
79.9, and H-1 of Gal at d 4.86 with C-3 at d
77.9 (C-3) (Figure 2). Finally, all analyses
above led us to determine the structure
of 1 as (25R)-26-O-b-D-glucopyranosyl-
furost-5-en-12-one-3b,22a,26-triol-3-O-
b-D-glucopyranosyl-(1 ! 2)-[b-D-xylo-
pyranosyl-(1 ! 3)]-b-D-glucopyranosyl-
(1 ! 4)-b-D-galactopyranoside, named
typaspidoside A.
3. Experimental
3.1 General experimental procedures
Optical rotations were measured with a
Perkin-Elmer 343 polarimeter (Perkin-
Elmer, Waltham, MA, USA). IR spectra
were recorded on a Vertex 70 spectrometer
(Bruker Optics, Billerica, Germany). The
Compound 2 was obtained as a white
amorphous powder. It was also suggested
to be a furostanol saponin based on its

528
J.-M. Cui et al.
NMR spectra were recorded with a Varian
UNITYINOVA 600 (599.8 MHZ for 1H
NMR and 150.8 MHZ for 13C NMR; Palo
Alto, CA, USA), with tetramethylsilane as
internal standard and pyridine-d5 as
solvent. The HR-ESI-MS was recorded
on Synapt MS system (Waters Corpor-
ation, Milford, MA, USA). Gas chromato-
graphic analyses were carried out by
using an Agilent 6890 system equipped
with a 5973 mass spectrograph detector
and an HP-5 capillary column (30 m £
0.25 mm £ 0.25 mm; Agilent, Milford,
MA, USA). MCI CHP20/P50 (Mitsubishi
Chemical, Tokyo, Japan), ODS silica gel
H2O for three times (2 h each time) by
reflux. The combined extracts were
evaporated to about 2 liters under reduced
pressure and the condensate was extracted
with isovolumetric n-BuOH for three
times. After removing the solvent from
the n-BuOH layer by concentrating and
freeze drying, the powder of total saponin
(92.0 g) was obtained. It was initially
separated by a silica gel and eluted with a
gradient mixture of CHCl3–MeOH (3:1,
2:1, 1:1) to give five fractions (A–E).
A part of fraction D (7.9 g) was
subjected to MCI CHP20/P50 column
chromatography and eluted with 30%
EtOH–H2O to produce 14 subfractions
(D1 –D14). Fraction D1 (1.12 g) was
chromatographed on an ODS silica gel
column with a gradient mixture of
MeOH–H2O (3:7, 7:13, 2:3, 9:11, and
8:2; 50 ml each tube) as eluent. A total of
150 tubes were collected. Then, tubes 74–
86 (94 mg) were combined and further
isolated by semi-preparative HPLC (col-
umn: 10 £ 250 mm, RP-18, 5 mm) with
MeOH–H2O (41:59, 4.0 ml/min) to give
compound 1 (34.9 mg, tR ¼ 42.9 min) and
compound 2 (15.3 mg, tR ¼ 39.4 min).
A part of fraction D6 (128.6 mg) was
purified by semi-preparative HPLC with
ACN–H2O (27:73, 4.0 ml/min) to afford
compound 3 (80.9 mg, tR ¼ 21.6 min).
˚
(120 A, 50 mm, YMC, Kyoto, Japan), and
silica gel H (Qingdao marine Chemical,
Qingdao, China) were used for chroma-
tography. Thin layer chromatography was
carried out on silica gel 60 plates (Merck,
Darmstadt, Germany). HPLC (Agilent
Technologies, Santa Clara, CA, USA)
was carried out using Agilent 1100 system:
an analytical column, ODS (5 mm,
4.6 £ 250 mm, Agela, Tianjin, China);
preparative column, an Agela Venusil
XBP C18 (5 mm, 10.0 £ 250 mm, Agela);
Shodex RID 102 detector (Showa Denko
Group, Tokyo, Japan); and Alltech eva-
porative light scattering detector (ELSD)
(evaporative light-scattering detector)
2100.
3.2 Plant material
3.3.1 Compound 1
The rhizomes of A. typica were harvested
from Xishuangbanna, Yunnan Province,
China in August 2011, and identified by
Prof. Li-xia Zhang (Yunnan Branch of
Institute of Medicinal Plant Development,
Chinese Academy of Medical Sciences). A
voucher specimen (No. 110820) has been
deposited in the Herbarium of Beijing
Institute of Radiation Medicine, Beijing.
20
White amorphous solid; ½aꢀD 262.5
(c 0.080, pyridine). IR (KBr) nmax: 3413,
2931, 1706, 1647, 1377, and 1073 cm21
.
1H NMR (pyridine-d5, 599.8 MHz) and
13C NMR (pyridine-d5, 150.8 MHz) spec-
tral data, see Table 1. ESI-MS (neg.): m/z
1093 [M–H–132]2, 1063 [M–H–162]2,
931 [M–H–132–162]2, 751 [M–H–
132–162–180]2, 589 [M–H–132–162–
162–180]2, and 427 [M–H–132–162–
162–180–162]2. HR-ESI-MS (neg.): m/z
1225.5457 [M–H]2 (calcd for C56H89O29,
1225.5490).
3.3 Extraction and isolation
The air-dried rhizome slices of A. typica
(2.0 kg) were extracted with 60% EtOH–

Journal of Asian Natural Products Research
529
Table 1. 1H and 13C NMR spectral data of compounds 1 and 2 (d in pyridine-d5).
1
2
Position
dC
dH J (Hz)
dC
dH J (Hz)
1
2
3
4
5
6
7
8
37.0
29.9
77.9
39.1
140.8
121.4
31.8
30.9
52.3
37.6
0.85 m, 1.45 oa
1.62 m, 2.03 o
3.82 m
2.37 m, 2.65 m
–
5.25 br s
1.44 o, 1.85 m
1.83 m
37.0
29.9
77.9
39.1
140.8
121.3
31.8
30.9
52.3
37.6
0.85 m, 1.45 o
1,63 m, 2.03 o
3.82 m
2.37 m, 2.65 m
–
5.25 br s
1.45 o, 1.84 m
1.83 m
9
10
1.28 m
–
1.28 m
–
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
37.6 2.27 dd (5.7, 14.5), 2.51 dd (13.3, 14.5)
37.6 2.27 dd (5.6, 14.7), 2.51 m
212.8
55.3
55.9
31.8
79.7
54.8
16.1
18.8
41.3
15.2
110.8
37.1
28.4
34.3
75.3
17.4
–
–
212.8
55.3
55.9
32.7
79.7
54.8
16.1
18.8
41.3
15.2
110.8
37.1
28.4
34.4
75.4
17.5
–
–
1.40 o
1.60 m, 2.06 m
4.86 o
2.93 dd (6.8, 8.4)
1.14 s
0.89 s
1.40 o
1.59 m, 2.06 m
4.85 o
2.92 dd (6.8, 8.6)
1.13 s
0.89 s
2.19 m
1.52 d (6.6)
–
1.95 m, 2.05 o
1.67 m, 2.04 o
1.92 m
2.19 m
1.53 d (6.6)
–
2.03 o
1.66 m, 2.03 o
1.91 m
3.60 dd (6.0, 9.6), 3.94 o
0.97 d (7.2)
3.49 dd (6.9, 9.3), 4.07 o
1.02 d (7.2)
27
Sugar part
Glc3
1
2
3
4
5
6
Gal
1
2
3
4
5
6
Xyl
1
2
3
4
Glc3
105.2
75.2
78.7
71.7
78.5
62.9
Gal
102.8
72.5
75.6
79.9
75.3
60.6
Xyl
105.0
75.1
78.7
70.8
67.4
Glc1
105.2
81.4
86.8
70.5
105.0
75.2
78.6
71.8
78.5
62.9
4.80 d (7.8)
4.01 t (7.8)
4.22 o
4.22 o
3.93 o
4.37 o, 4.54 o
4.80 d (7.8)
4.01 t (7.8)
4.23 o
4.22 o
3.93 o
4.37 o, 4.53 o
102.8
73.2
75.6
79.9
75.4
60.6
4.86 d (7.8)
4.41 o
4.09 o
4.58 o
3.95 o
4.16 o, 4.65 m
4.86 d (7.8)
4.40 o
4.08 o
4.58 o
3.95 o
4.16 o, 4.65 m
105.0
75.1
78.7
70.8
67.4
5.22 d (7.8)
3.95 o
4.06 o
5.23 d (7.8)
3.95 o
4.07 o
4.09 o
3.66 t (10.5), 4.21 o
4.10 o
3.66 t (10.6), 4.21 o
5
Glc1
1
2
3
105.2
81.4
86.8
70.5
5.18 d (8.4)
4.42 t (8.4)
4.16 o
5.18 d (8.4)
4.42 t (8.4)
4.16 o
4
3.81 m
3.80 m

530
J.-M. Cui et al.
Table 1 – continued
1
2
Position
dC
dH J (Hz)
dC
dH J (Hz)
5
6
Glc2
1
2
3
4
5
6
77.6
63.0
3.87 m
4.04 o, 4.50 m
77.6
63.0
Glc2
104.9
76.3
77.8
71.1
78.8
62.5
3.87 m
4.03 o, 4.51 o
104.9
76.2
77.7
71.1
78.8
62.5
5.57 d (7.8)
4.06 o
4.11 o
4.19 o
3.92 o
4.36o, 4.56 o
5.57 d (7.8)
4.06 o
4.11 o
4.19 o
3.92 o
4.36 o, 4.56 o
a Overlapped with other signals.
3.3.2 Compound 2
analyzed by GC under the following
conditions: Agilent Technologies 6890
gas chromatograph equipment; 5973
mass spectrograph detector; HP-5 capil-
lary column (30 m £ 0.25 mm £ 0.25 mm);
column temperature: 1808C–2508C, pro-
grammed increase, 158C/min; carrier gas:
N2 (1 ml/min); injection and detector
temperature: 2508C; injection volume:
1.0 ml; split ratio: 1/50. Ultimately, the
D-configurations of glucose, galactose, and
xylose were determined by comparing
their retention times with those of standard
samples, respectively. tR: D-glucose
(17.93, 19.67 min), D-xylose (13.01,
14.77 min), and D-galactose (18.54,
20.24 min).
20
White amorphous solid; ½aꢀD 253.3 (c
0.060, pyridine). IR (KBr) nmax: 3420,
2931, 1707, 1646, 1377, and 1073 cm21
.
1H NMR (pyridine-d5, 599.8 MHz), and
13C NMR (pyridine-d5, 150.8 MHz) spec-
tral data, see Table 1. ESI-MS (neg.): m/z
1093 [M–H–132]2, 1063 [M–H–162]2,
931 [M–H–132–162]2, 751 [M–H–
132–162–180]2, 589 [M–H–132–162–
162–180]2, and 427 [M–H–132–162–
162–180–162]2. HR-ESI-MS (neg.): m/z
1225.5453 [M–H]2 (calcd for C56H89O29,
1225.5490).
3.4 Acid hydrolysis ofcompounds 1and 2
Compounds 1 (2.7 mg) and 2 (2.2 mg)
were separately treated with 2N aq.
CF3COOH (5 ml) at 958C for 2.5 h. The
cooled hydrolysate was extracted with
CH2Cl2 (5 ml) for three times. The
aqueous phase was concentrated to dry-
ness with EtOH to yield the sugar residue.
Then it was dissolved in anhydrous
pyridine (2 ml), and L-cysteine methyl
ester hydrochloride (12 mg) was added.
The mixture was stirred at 608C for 1 h.
Furthermore, (hexamethyldisilazane–tri-
methylchlorosilane, 2:1; 6 ml) was added
and preserved at 608C for another 0.5 h
[19]. In the end, the supernatant was
Acknowledgments
This investigation was financially supported by
the Major Program of Municipal Natural
Science Foundation of Beijing (7090001). The
authors are grateful to Miss Mei-Feng Xu of the
National Center of Biomedical Analysis for
measurements of the NMR spectra.
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