Phenolic glycosides isolated from the bark of Lysidice brevicalyx Wei

Article abstract of DOI:10.1080/10286020.2010.489818

Two new compounds, lysidiside S (1) and 7-O-(+)-peltogynol-β-D- glucopyranoside (2), together with six known phenolic glycosides (3-8) were isolated from the bark of Lysidice brevicalyx Wei. The structures of these compounds were characterized by chemical

Full text of DOI:10.1080/10286020.2010.489818

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Phenolic glycosides isolated from the
bark of Lysidice brevicalyx Wei
You-Cai Hu a , Shuang-Gang Ma a , Shi-Shan Yu a , Xian-Fu Wu a
Yong Li a
&
a Key Laboratory of Bioactive Substances and Resources Utilization
of Chinese Herbal Medicine, Ministry of Education , Institute of
Materia Medica, Chinese Academy of Medical Sciences and Peking
Union Medical College , Beijing, 100050, China
Published online: 15 Jun 2010.
To cite this article: You-Cai Hu , Shuang-Gang Ma , Shi-Shan Yu , Xian-Fu Wu & Yong Li (2010)
Phenolic glycosides isolated from the bark of Lysidice brevicalyx Wei, Journal of Asian Natural
Products Research, 12:6, 516-521, DOI: 10.1080/10286020.2010.489818
To link to this article: http://dx.doi.org/10.1080/10286020.2010.489818
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Journal of Asian Natural Products Research
Vol. 12, No. 6, June 2010, 516–521
ORIGINAL ARTICLE
Phenolic glycosides isolated from the bark of Lysidice brevicalyx Wei
You-Cai Hu, Shuang-Gang Ma, Shi-Shan Yu*, Xian-Fu Wu and Yong Li
Key Laboratory of Bioactive Substances and Resources Utilization of Chinese Herbal Medicine,
Ministry of Education, Institute of Materia Medica, Chinese Academy of Medical Sciences and
Peking Union Medical College, Beijing 100050, China
(Received 7 December 2009; final version received 26 April 2010)
Two new compounds, lysidiside S (1) and 7-O-(þ)-peltogynol-b-D-glucopyranoside
(2), together with six known phenolic glycosides (3–8) were isolated from the bark
of Lysidice brevicalyx Wei. The structures of these compounds were characterized
by chemical and spectroscopic methods. The antioxidant activities of compounds
1–8 were evaluated, and compound 3 exhibited remarkable antioxidant activity
at concentrations of 1024, 1025, and 1026 mol/l.
Keywords: Lysidice brevicalyx; lysidiside S; 7-O-(þ)-peltogynol-b-D-glucopyrano-
side; antioxidant
1. Introduction
capacity of compounds 1–8 was evaluated
in vitro.
Lysidice brevicalyx Wei belongs to the
genus Lysidice in the family Fabaceae [1].
During our previous studies on bioactive
constituents from the genus Lysidice, we
obtained bioactive stilbenes, phlorogluci-
nols, flavanoids, and lignans [2–9].
Recently, a procedure based on biological
and chemical screening has been used to
investigate the antioxidant constituents
from the bark of L. brevicalyx, and seven
new stilbene glycosides were obtained
2. Results and discussion
Compound 1 was obtained as an amor-
phous powder, and the presence of OH
(3229 cm21), conjugated carbonyl esters
(1697 cm21), and aromatic rings (1596 and
1512 cm21) were indicated by its IR
spectrum. The molecular formula of
compound 1 was determined to be
C28H28O10 by negative HR-ESI-MS.
Absorption maximum at 210, 310, and
320 nm in its UV spectrum were indicative
of a stilbene moiety [10]. The presence of
(E)-resveratrol moiety in compound 1 was
supported by its 1H NMR signals (Table 1)
at dH 6.33 (1H, br s), 6.58 (1H, br s), 6.64
(1H, br s), 7.33 (2H, d, J ¼ 8.5 Hz), 6.73
(2H, d, J ¼ 8.5 Hz), 6.81 (1H, d,
J ¼ 16.0 Hz), and 6.98 (1H, d,
J ¼ 16.0 Hz). A detailed analysis of the
from an antioxidant fraction (Fr. C2–3
)
[10]. As part of our continuing program for
targeted isolation of novel bioactive
constituents from a natural source, we
carried out an investigation of constituents
of other subfractions from the title plant.
Eight compounds, 1–8 (Figure 1), includ-
ing one new stilbene glycoside (1), one
new flavanol glycoside (2), and six known
compounds were isolated. The antioxidant
*Corresponding author. Email: yushishan@imm.ac.cn
ISSN 1028-6020 print/ISSN 1477-2213 online
q 2010 Taylor & Francis
DOI: 10.1080/10286020.2010.489818
http://www.informaworld.com

Journal of Asian Natural Products Research
517
3'
2'
1'
R1
Me
HO
O
2'
3'
β
5
3'''
6
4'
2'''
1'''
6'''
HO
HO
O
OH
O
β
7'''
5
4' OH
6
3'''
HO4'''
2'''
4
7'''
O
α
1'
1
6'
5'
4'''
5'''
4
O
5'
6''
3
4''
1'''
α
6'
5'''
R2
1
2
5''
O
6''
3
O
1''
4''
6'''
O
1''
2
5''
O
HO
HO
2'' OH 3 R1 = OMe, R2 = H
4 R1 = R2 = H
3''
HO
2'' OH
1
3''
5 R1 = R2 = OMe
2a
8
1
2
MeO
7
6
R1
HO
OH
3'' OH
9
2''
3'
OH
R2
O
6''
4
3
1''
2'
1'
OH
O
4''
10
HO
OH
4''
4'
5'
O
5
1
O
5''
6''
3a
5''
8
5
HO
HO
8a
O
7
OMe
6'
1'
2'
O
2
6'
7'
2'' OH1''
4
3''
3
7'''
1'''
O
6
3'
4a
O
5'
MeO
OMe
4'
6'''
2'''
3'''
OMe
OH
OH
R
2 R1 = OH, R2 = H
8 R1 = H, R2 = OH
5'''
4'''
6 R = OMe
7 R = H
OH
Figure 1. Structures of compounds 1–8.
NMR spectra of compound 1 with the help
of 1H–1H COSY and HMBC experiments
revealed the presence of a 2-methoxyben-
zoyl ester and a glucopyranoside unit,
besides the resveratrol moiety. The presence
of a downfield methylene signal at dC 63.9
(C-600) in its 13C NMR spectrum established
the attachment of a 2-methoxybenzoyl ester
moiety at C-600 of glucose, which was
further confirmed by the HMBC correlation
(Figure2) from H-600 atdH 4.23toC-7000 atdC
165.1. HMBC correlation between the
anomeric proton at dH 4.93 (H-100) and C-3
at dC 158.6 indicated the location of a
glucose unit at C-3 of the aglycone. Acid
hydrolysis of compound 1, followed by the
HPLC analysis [10,11], indicated the pre-
sence of D-glucose. The large coupling
constant for the anomeric proton (8.0Hz)
indicated b-configuration for glucose. As a
result, the structure of compound 1 was
determined to be (E)-3,5,40-trihydroxystil-
bene 3-O-[6-O-(2-methoxy)-benzoyl]-b-D-
glucopyranoside, named lysidiside S.
The 1H NMR spectrum (Table 2) of
compound 2 showed signals due to a 1,3,4-
trisubstituted phenyl group and a 1,2,4,5-
tetrasubstituted phenyl group. In addition,
it showed signals attributed to three
oxymethine protons at dH 4.67 (H-4),
4.81 (H-2), and 4.83 (H-100), one methyl-
ene proton at d 4.69 (H-70), partially
overlapped methylene and methine pro-
tons at dH 3.20–3.70 and signals due to
five OH protons between dH 4.50 and 5.80,
and two phenolic OH protons at dH 9.01.
Besides the carbon resonance correspond-
ing to the above-mentioned phenyl units,
the 13C NMR and DEPT spectra of
compound 2 displayed carbon signals
attributed to eight oxymethines between
dC 69.7 and 100.5, and two oxymethylenes
at d 66.99 (C-70) and 60.7 (C-600). These
spectroscopic data suggested that com-
pound 2 was a flavanol glycoside with an
aglycone possessing 16 carbons, similar to
mopanolside (8) [2]. The proton signals at
dH 6.46 (1H, s, H-50) and 6.93 (1H, s, H-20)
indicated the presence of a 1,2,4,5-
tetrasubstituted phenyl unit in ring B of
compound 2, which was confirmed by
HSQC and HMBC experiments (Figure 3).
HMBC correlation between the anomeric
proton at dH 4.83 and C-7 at dC 157.6
Compound 2 was obtained as a pale
yellow powder, and its molecular formula,
C22H24O11, was indicated by HR-ESI-MS.
The IR spectrum of compound 2 displayed
absorption bands for OH (3401 cm21) and
aromatic (1584 and 1521 cm21) moiety.

518
Y.-C. Hu et al.
d
d
d
d
d
d

Journal of Asian Natural Products Research
519
CH3
O
OH
HO
O
O
OH
OH
OH
O
O
O
O
HO
HO
O
HO
HO
OH
O
OH
OH
HMBC
1H–1H COSY
(→HMBC correlations)
Figure 2. Key HMBC and 1H–1H COSY
correlations of compound 1.
Figure 3. Key HMBC correlations of
compound 2.
indicated the location of a glucose unit at
C-7 of the aglycone. Acid hydrolysis
of compound 2, followed by HPLC
analysis [2,10,11], indicated the presence
of D-glucose. The large coupling constant
for the anomeric proton (8.0 Hz) indicated
b-configuration for glucose.
showed an ABX system for: dH 4.81 (1H, d,
J ¼ 9.5 Hz, H-2), 4.67 (1H, dd, J ¼ 7.5,
7.5 Hz, H-4), and 3.44 (1H, dd, J ¼ 9.5,
7.5 Hz, H-3), which revealed the relative
configuration of C-2–C-4, as shown in
Figure 3. The absolute configuration of C-2
was determined from the CD spectrum. The
negative Cotton effect at 283 nm revealed
the R configuration for C-2 [12,13]. Thus,
the structure of compound 2 was assigned as
The stereochemistry of compound 2
was unequivocally determined on the basis
1
of H NMR spectrum and circular dichro-
1
ism (CD) spectrum. Its H NMR spectrum
7-O-(þ)-peltogynol-b-D-glucopyranoside.
Compounds 3 and 4 have been
Table 2. 1H NMR (500 MHz) and 13C NMR
(125 MHz) spectral data for compound 2 in
DMSO-d6.
detected in this plant and their structures
were assigned on the basis of LC-MSn and
LC-HRMS analysis [9]. However, no
spectral NMR data of them were reported
earlier. In this paper, the spectral NMR
data of compounds 3 and 4 are presented in
Table 1. The known compounds 5 [14], 6
[15], 7 [16], and 8 [2] were identified by
comparing their spectroscopic data with
Position
dC
dH (J in Hz)
2
3
4
71.8
77.5
68.0
4.81 d (9.5)
3.44 dd (9.5, 7.5)
4.67 dd (7.5, 7.5)
4a
5
6
7
8
120.0
129.1
109.9
157.6
103.2
154.3
122.6
112.6
144.3
145.2
110.5
125.5
66.99
100.5
73.2
7.35 d (8.5)
6.66 dd (2.0, 8.5)
6.50 d (1.5)
6.93 s
8a
10
those of the literature values.
The in vitro antioxidant activities of
20
30
compounds 1–8 were evaluated in a
parallel experiment by measuring their
inhibition activity on the liver microsomal
40
50
6.46 s
600
lipid peroxidation induced by Fe2þ
-
700
4.69 s
1
4.83 d (8.0)
3.21 m
3.25 m
3.16 m
3.32 m
3.69 m, 3.46 m
5.75 d (7.5)
9.00 br s
9.00 br s
Cysteine system in vitro with vitamin E
as a positive control. Compounds 1, 3–5,
and 7–8 showed clear activities at the
concentration of 1024 M (Table 3). Par-
ticularly, compound 3 also showed obvious
antioxidant activity at concentrations of
1025 and 1026 M.
200
300
76.5
69.7
77.7
60.7
400
500
600
4-OH
30-OH
40-OH

520
Y.-C. Hu et al.
3.3 Extraction and isolation
Table 3. Antioxidant activity of compounds
1–8.
The extraction and isolation procedures
were successive to those reported pre-
viously [10]. The antioxidant fraction C2–1
(7.0g) was submitted to an ODS column
(50 mm, 300 g) and purified by preparative
HPLC using 25% MeCN–H2O (5ml/min)
to yield compounds 5 (89 mg, tR ¼ 38min)
and 6 (72 mg, tR ¼ 55min). Fraction C2–2
(3.4g) was submitted to an ODS column
(50 mm, 100 g) and purified by preparative
HPLC using 20% MeCN–H2O (5ml/min)
to yield compounds 7 (33 mg, tR ¼ 33min)
and 8 (90 mg, tR ¼ 42 min). Subfraction C3
(38.3 g) was submitted to an ODS column
(50 mm, 200 g) and eluted with a gradient of
MeOH–H2O (10:90–80:20), and further
separated by Sephadex LH-20 (130 g,
1.5 m £ 2 cm, eluted with MeOH) and
preparative HPLC (45% MeOH–H2O;
5 ml/min) to give compounds 1 (24 mg), 2
(61 mg), 3 (6 mg), and 4 (33 mg).
Restrainability (%)
Compound
1024
M
1025
M
1026
M
1
2
3
4
5
6
7
115.2
41.7
113.8
115.9
84.2
36.1
93.2
80.9
81.5
22.9
0
62.1
35.3
1.5
2.1
6.1
12.2
33.4
0
0
15.7
0
0
0
0
0
0
8
VEa
Note: a As positive control.
3. Experimental
3.1 General experimental procedures
Optical rotations were recorded on a Perkin-
Elmer 241 automatic digital polarimeter. IR
spectra were recorded on a Nicolet 5700 FT-
IR spectrometer by a microscope trans-
mission method. CD spectra were recorded
on a JASCO-712 polarimeter. NMR spectra
were obtained on an INOVA-500 spec-
trometer with solvent peaks being used as
references. ESI-MS data were measured
with an Agilent 1100 Series LC/MSD Trap
mass spectrometer. HR-ESI-MS data were
measured using a Micromass Autospec-
Ultima ETOF spectrometer. Preparative
HPLC was performed on a Shimadzu LC-
6AD instrument with an SPD-10A detector,
using YMC-Pack ODS-A column
(250 £ 20mm, 5 mm). Polyamide (30–60
mesh, Jiangsu Linjiang Chemical Reagents
Factory, Lingjing, China) and ODS (50 mm,
Merck, Darmstadt, Germany) were used for
column chromatography.
3.3.1 Lysidiside S (1)
20
White powder (24 mg); ½aꢀD þ53.60
(c ¼ 0.005, MeOH); UV (MeOH) lmax
210, 310, 320 nm; IR nmax 3229, 1697,
1596, 1512, 1463, 1434, 1370, 1246, 1076,
1
1016, 961, 752 cm21; H and 13C NMR
spectral data, see Table 1; HR-ESI-MS m/z
523.1612 [M 2 H]2 (calcd for C28H27O10,
523.1604); ESI-MS m/z 523 [M 2 H]2.
3.3.2 7-O-(þ)-Peltogynol-b-D-glucopy-
ranoside (2)
20
Pale yellow powder (33 mg); ½aꢀD þ94.5
(c ¼ 0.06, MeOH); UV (MeOH) lmax 201,
225, 280 nm; IR nmax 401, 2887, 1616,
1584, 1521, 1497, 1281, 1065, 1015, 888,
793 cm21; 1H and 13C NMR spectral data,
see Table 2; HR-ESI-MS m/z 463.1249
[M 2 H]2 (calcd for C22H23O11,
463.1240); ESI-MS m/z 463 [M 2 H]2.
3.2 Plant material
The bark of L. brevicalyx was collected
from Guangxi Province, China, and
identified by Professor Songji Wei in
September 2006. A voucher specimen has
been deposited in the Herbarium of the
Department of Medicinal Plants, Institute
of Materia Medica.
3.4 Antioxidant assays
The antioxidant assays were performed
according to the reported procedures [10].

Journal of Asian Natural Products Research
521
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control. The activities were determined by
measuring the content of malondialdehyde
(MDA), a compound produced during
microsomal lipid peroxidation induced
by Fe2þ-cysteine. MDA was detected
using the thiobarbituric acid method.
The inhibition rate was calculated
as 100% 2 At/(Ap 2 Ac) £ 100, where Ap,
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Acknowledgements
The research project was supported by the
National Fund for Distinguished Young Scho-
lars (No. 30625040) and National Key Basic
R&D (973) Project (No. 2004CB518906). We
thank the Department of Medicinal Analysis,
Institute of Materia Medica, Chinese Academy
of Medical Sciences for the measurements of
IR, NMR, and MS spectra, and the Department
of Pharmacology of our institute for antioxida-
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