Three new compounds from the leaves of Liquidambar formosana

Article abstract of DOI:10.1080/10286020.2013.837456

Two new flavan glycosides, (2S)-5,7,4′-trihydroxyflavan-7-O-β-d- glucopyranoside (1) and (2S)-5,7,4′-trihydroxyflavan-5-O-β-d- glucopyranoside (2), and a new neolignan, (7S,8S)-3-methoxyl-3′-O-β- d-glucopyrannosyl-4′:8,5′:7-diepoxyneolignan-4,9′-diol (3), were isolated from the leaves of Liquidambar formosana Hance. Their structures were elucidated on the basis of spectroscopic data and chemical evidence.

Full text of DOI:10.1080/10286020.2013.837456

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Three new compounds from the leaves
of Liquidambar formosana
a
ab
a
a
Rui-Jian Zhong , Hui Yuan , Hui-Zheng Fu , Guo-Ping Zhou , Xin
a
a
ab
Wu , Chun-Hua Zhang & Ming-Ming Yuan
a
Jiangxi Provincial Institute for Drug and Food Control, Nanchang,
30029, China
3
b
Pharmaceutical Department, Nanchang University, Nanchang,
30006, China
3
Published online: 11 Nov 2013.
To cite this article: Rui-Jian Zhong, Hui Yuan, Hui-Zheng Fu, Guo-Ping Zhou, Xin Wu, Chun-Hua
Zhang & Ming-Ming Yuan (2013) Three new compounds from the leaves of Liquidambar formosana,
Journal of Asian Natural Products Research, 15:12, 1249-1255, DOI: 10.1080/10286020.2013.837456
To link to this article: http://dx.doi.org/10.1080/10286020.2013.837456
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Journal of Asian Natural Products Research, 2013
Vol. 15, No. 12, 1249–1255, http://dx.doi.org/10.1080/10286020.2013.837456
Three new compounds from the leaves of Liquidambar formosana
a
Rui-Jian Zhong , Hui Yuan , Hui-Zheng Fu *, Guo-Ping Zhou *, Xin Wu ,
a,b
a
a
a
a
Chun-Hua Zhang and Ming-Ming Yuan
a,b
a
Jiangxi Provincial Institute for Drug and Food Control, Nanchang 330029, China;
Pharmaceutical Department, Nanchang University, Nanchang 330006, China
b
(Received 14 May 2013; final version received 20 August 2013)
0
and (2S)-5,7,4 -trihydroxyflavan-5-O-b-D-glucopyranoside (2), and a new neolignan,
Two new flavan glycosides, (2S)-5,7,4 -trihydroxyflavan-7-O-b-D-glucopyranoside (1)
0
0
0
0
0
(
7S,8S)-3-methoxyl-3 -O-b-D-glucopyrannosyl-4 :8,5 :7-diepoxyneolignan-4,9 -diol
3), were isolated from the leaves of Liquidambar formosana Hance. Their structures
(
were elucidated on the basis of spectroscopic data and chemical evidence.
Keywords: Liquidambar formosana; flavan glycosides; neolignan
1
.
Introduction
the isolation and elucidation of three new
compounds.
Liquidambar formosana Hance, belonging
to the family Hamamelidaceae, is widely
distributed in China, Laos, North Korea,
Vietnam, and Japan, and it is known for its
resins [1]. Its leaves are used in folk
medicine for treating dysentery, diarrhea,
hemostasis, and detoxification [2]. Previous
phytochemical studies on this plant have led
to the isolation and identification of several
flavonoids, triterpenoids, and tannins [1,3–
2
.
Results and discussion
The leaves of L. formosana were collected
from Yiyang, Jiangxi Province, China and
identified by Prof. Guiping Yuan, Jiangxi
Provincial Institute for Drug and Food
Control. The H O extract of the leaves of
2
L. formosana was fractionated by different
solvents, among which the EtOAc fraction
displayed significant antimicrobial activity
at a concentration of 10 mg/ml. The EtOAc
fraction was subjected to separation using
various column chromatography (CC)
techniques to afford three new compounds
8
]. Up to date, there are few reports on the
chemical constituents or bioactive com-
pounds from the leaves of L. formosana. In
ourpreliminaryscreening, theEtOAcpartof
the H O extract from the leaves of
2
L. formosana showed antimicrobial activity.
As part of a program to discover significant
antimicrobical properties from plant
resources has led to the isolation of three
(
1–3).
Compound 1 was obtained as a white
amorphous powder. The molecular for-
mula C H O was determined by HR-
2
1 24 9
0
þ
new compounds, (2S)-5,7,4 -trihydroxyfla-
van-7-O-b-D-glucopyranoside (1), (2S)-
TOF-MS (m/z 421.1496 [M þ H] , calcd
for 421.1493) and supported by NMR
spectroscopic data. The UV spectrum
0
5
anoside (2), and (7S,8S)-3-methoxyl-3 -O-
,7,4 -trihydroxyflavan-5-O-b-D-glucopyr-
0
showed absorption maxima at 271 nm.
1
0
0
b-D-glucopyrannosyl-4 :8,5 :7-diepoxy-
0
The H NMR spectrum of 1 in CD OD
3
0 0
exhibited a set of AA BB system at d
H
neolignan-4,9 -diol (3), from the leaves of
L. formosana (Figure 1). We report herein
7.21 (2H, d, J ¼ 8.4 Hz) and 6.77 (2H, d,
*Corresponding authors. Email: fhzfhz620@sohu.com
q 2013 Taylor & Francis

1
250
R.-J. Zhong et al.
3
'
OH
1
'
R O
9
O
4
1
5'
7
2
5
OR2
HO
1
2
R =G lc, R =H
O
1
2
Glc = HO
HO
R =H , R =G lc
1
2
OH
OH
OH
OH
HO
O
1
''
O
9
3
'
8
O
O
HO
8
'
7
OH
5
1'
5
'
1
7'
9'
HO
3
OCH3
3
Figure 1. Chemical structures of compounds 1–3.
J ¼ 8.4 Hz), two meta-coupled aromatic
unit is located at C-7. In the NOESY
0
0
protons at d 6.23 (1H, d, J ¼ 2.0 Hz) and
spectrum, Glc-H-1 (dH 4.86) showed
correlations with H-6 (dH 6.23) and H-8
(dH 5.99), further indicating that the
glucose unit is attached to C-7. Based on
the known 2S absolute configuration of
S-3,4-dihydro-2-phenyl-2H-1-benzopyran
H
5
proton at d 4.86 (1H, overlap) correlated
.99 (1H, d, J ¼ 2.0 Hz), and an anomeric
H
with one anomeric carbon at d 102.8 in
C
1
3
the HSQC spectrum. The
spectrum of 1 displayed 21 carbon signals,
C NMR
of which 6 were assigned to the sugar
13
[11–13], and the same fact that a negative
1
Cotton effect ascribed to the L transition
1
moiety. Comparison of its H and
C
b
0
NMR spectral data with those of 5,7,4 -
trihydroxyflavan suggested that they have
the same framework [9]. The structural
difference is that there is an additional
sugar unit in compound 1. Acid hydrolysis
of 1 with 2 M HCl afforded D-glucose,
which was identified by GC analysis of
their trimethylsilyl L-cysteine derivatives
at 277 nm was observed in the CD
spectrum of 1, the absolute configuration
at C-2 was assigned as S. Thus, compound
0
1 was elucidated as (2S)-5,7,4 -trihydrox-
yflavan-7-O-b-D-glucopyranoside.
Compound 2 was obtained as a white
amorphous powder, It had the same
molecular formula as 1, namely
C H O , as deduced by HR-TOF-MS
[10]. In the HMBC spectrum, the presence
of correlation from Glc-H-1 (d 4.86) to
2
1 24 9
00
2
(m/z 419.1311 [M–H] , calcd for
419.1323). The NMR spectroscopic data
H
C-7 (d 158.1) confirmed that the glucose
C

Journal of Asian Natural Products Research
1251
of 2 were almost identical with those of 1.
The only difference between 2 and 1 is the
linkage position of glucose. In the HMBC
spectrum of 2, a long-range correlation
dihydrobenzofuran skeleton. Significant
HMBC correlations were observed between
H-6/C-7, H-7/C-6, H-8/C-7, H-8/C-9, H-8/
0
C-4 , and OCH /C-3 (Figure 2). From the
3
0
0
from Glc-H-1 (d 4.84) to C-5 (d 157.8)
C
foregoing pieces of evidence, the skeleton
of 3 could be concluded as 3-methoxyl-
H
confirmed that the glucose unit is located
00
0
0
0
at C-5. In the NOESY spectrum, Glc-H-1
dH 4.84) exhibited a clear correlation with
H-6 (d 6.24), while no NOE correlation
4 :8,5 :7-diepoxyneolignan-4,9 -diol.
(
Acid hydrolysis of 3 with 2 M HCl
afforded D-glucose, which was identified
by GC analysis of their trimethylsilyl L-
cysteine derivatives [10]. On the basis of
the coupling constant of anomeric proton
and the chemical shift of the anomeric
carbon, the anomeric configuration of the
glucose moiety was determined as b [15].
The proton and protonated carbon signals
in the NMR spectra of 3 were assigned
H
0
0
of Glc-H-1 / H-8 was observed, further
suggesting that the glucose unit is attached
to C-5. The CD spectrum of 2 displayed a
negative Cotton effect at 276 nm, similar
to compound 1, and the absolute configur-
ation of C-2 in compound 2 was
determined to be S. Thus, compound 2
0
was determined as (2S)-5,7,4 -trihydroxy-
flavan-5-O-b-D-glucopyranoside.
1
1
unequivocally on the basis of H– H
COSY and HSQC spectroscopic analyses.
In the HMBC spectrum of 3, a long-range
Compound 3 was obtained as a white
amorphous powder, and its positive-ion
HR-TOF-MS gave a quasi-molecular ion
0
0
0
correlation from Glc-H-1 (d 4.94) to C-3
H
þ
peak at m/z 525.1973 [M þ H] , which
(d 144.4) confirmed that the glucose unit is
C
0
indicated the molecular formula to be
C H O . The UV spectrum showed an
attached to C-3 (Figure 2). The relative
configuration of H-7 and H-8 was trans
2
5 32 12
1
absorption maximum at 278 nm. The H
1
from the J7,8 value of 7.2 Hz in the H NMR
NMR spectrum of 3 in DMSO-d exhib-
6
spectrum. The absolute configurations of
C-7andC-8weredeterminedas7S,8Sonthe
basis of the positive Cotton effect at 238nm
in the CD spectrum [16–19]. Therefore,
compound 3 was characterized as (7S,8S)-3-
ited the following proton signals: ABX-
type aromatic protons at dH 6.98 (1H, d,
J ¼ 3.6 Hz), 6.82 (1H, dd, J ¼ 7.8,
3
.6 Hz), and 6.79 (1H, d, J ¼ 7.8 Hz);
0
0
two meta-coupled aromatic protons at dH
.55 (1H, d, J ¼ 1.8 Hz) and 6.39 (1H, d,
methoxyl-3 -O-b-D-glucopyrannosyl-4 :
0 0
8,5 :7-diepoxyneolignan-4,9 -diol.
6
J ¼ 1.8 Hz); a hydroxypropyl group at d
H
2
3
.45–2.48 (2H, m), 1.65–1.68 (2H, m),
.47 (1H, dd, J ¼ 12.0, 6.6 Hz), and 3.65
3
.
Experimental
3
.1 General experimental procedures
(1H, d, J ¼ 12.0 Hz); a moiety of (ph) CH
(O)ZCH(O)ZCH OZ [d 4.87 (1H, d,
2
Optical rotations were measured on an
Autopol IV-T/V (Rudolph Research Ana-
lytical, New Jersey, NJ, USA). UV spectra
were recorded in MeOH on a Jasco V650
spectrophotometer (JASCO, Inc., Easton,
Maryland, USA). CD spectra were
measured on a MOS-450/AF-CD (Bio-
H
J ¼ 7.2 Hz), 4.04–4.07 (1H, m), 3.39 (1H,
t, J ¼ 6.6 Hz), 3.33 (1H, dd, J ¼ 12.0,
4.2 Hz)]; a methoxyl singlet at d 3.77 (3H,
s); and an anomeric signal of a sugar unit at
dH 4.94 (1H, d, J ¼ 7.2 Hz). The carbon
1
3
signals in the C NMR spectrum of 3
further confirmed the above units. Com-
parison of the NMR spectroscopic data of 3
with those of (7R,8R)-3-methoxyl-9-O-b-
1
Logic, Claix, France). The H (600 MHz),
1
C (150 MHz) and 2D NMR spectra were
3
recorded on a Bruker AVANCE III 600
instrument using tetramethylsilane as an
internal reference (Bruker Company, Bill-
erica, MA, USA). ESI-MS data were
0
0
D-xylopyranosyl-4 :7,5 :8-diepoxyneodie-
0
poxyneolignan-4,9 -diol [14] demonstrated
that the aglycone part of 3 was likely to be a

1
252
R.-J. Zhong et al.
Figure 2. Key HMBC (H ! C) correlations of compounds 1–3.
collected on a HPLC-MS ZQ4000/2695
instrument (Waters Company, Milford,
MA, USA). HR-TOF-MS data were
obtained on an Agilent 7890-7000A mass
spectrometer (Agilent Technologies, Santa
Clara, CA, USA). Preparative HPLC was
conducted with an Agilent Technologies
3.2 Plant material
The leaves of L. formosana were collected
from Yiyang, Jiangxi Province, China, in
May 2012 and were identified by Prof.
Guiping Yuan at Jiangxi Provincial
Institute for Drug and Food Control,
China.
2
A
0120516) has been deposited in the
voucher specimen (No.
1
200 series instrument with an multiple
Herbarium of Jiangxi Provincial Institute
for Drug and Food Control.
wavelength detector using a YMC-pack
ODS (Octadecylsilyl)-A column (10 mm,
2
50 £ 20 mm). CC was carried out with
silica gel (200–300 mesh, Qingdao Marine
Chemical Ltd, Qingdao, China), Develosil
ODS (50 mm, Nomura Chemical Co. Ltd,
Osaka, Japan), Sephadex LH-20 (GE
Healthcare Bio-Sciences AB, Uppsala,
Sweden). TLC (thin-layer chromatog-
raphy) was carried out with glass pre-
coated with silica gel GF254. Spots were
visualized under UV light or by spraying
with 10% sulfuric acid in EtOH followed
by heating.
3
.3 Extraction and isolation
The powdered dried leaves of L. formo-
sana (12.0 kg) were extracted with H O at
2
reflux for 3 £ 3 h. The extracted solution
was evaporated under reduced pressure to
yield a dark residue (2.1 kg), which was
suspended in H O (16 liters) and then
2
partitioned with CHCl3 (3 £ 16 liters),
EtOAc (3 £ 16 liters), and n-BuOH
(3 £ 16 liters), successively. After remov-
ing the solvent, the EtOAc-soluble portion

Journal of Asian Natural Products Research
1253
1 13
Table 1. H NMR (600 MHz) and C NMR (150 MHz) spectral data of compounds 1 and 2 in
CD OD (d in ppm, J in Hz).
3
1
2
Position
d
H
d
C
Position
d
H
d
C
2
3
4.88 (1H, overlap)
2.71–2.73 (2H, m)
78.3
20.5
2
3
4.82 (1H, overlap)
1.88–1.93 (1H, m)
77.4
20.6
2
.87–2.92 (1H, m)
4
1.91–1.95 (1H, m)
.09–2.11 (1H, m)
30.7
4
2.08–2.11 (1H, m)
2.60–2.65 (1H, m)
30.8
2
5
6
7
8
9
1
1
2
3
4
5
6
158.0
96.8
158.1
99.0
5
6
7
8
9
10
157.8
96.7
157.9
98.7
6.23 (1H, d, 2.0 Hz)
5.99 (1H, d, 2.0 Hz)
6.24 (1H, d, 2.4 Hz)
5.85 (1H, d, 2.4 Hz)
157.9
105.7
133.5
128.6
116.3
158.4
116.3
128.6
102.8
75.1
158.0
105.2
134.4
128.6
116.2
158.3
116.2
128.6
102.7
75.1
0
0
0
1
2
3
4
0
0
0
0
0
0
7.21 (1H, d, 8.4 Hz)
6.77 (1H, d, 8.4 Hz)
7.22 (1H, d, 7.8 Hz)
6.77 (1H, d, 7.8 Hz)
0
0
0
6.77 (1H, d, 8.4 Hz)
7.21 (1H, d, 8.4 Hz)
4.86 (1H, overlap)
5
6.77 (1H, d, 8.4 Hz)
7.22 (1H, d, 8.4 Hz)
4.84 (1H, d, 7.8 Hz)
3.45–3.46 (1H, m)
3.43–3.44 (1H, m)
3.40–3.42 (1H, m)
3.43–3.44 (1H, m)
3.73 (1H, dd, 11.0, 4.8 Hz)
3.91 (1H, d, 11.0 Hz)
0
Glc-1
6
0
0
00
Glc-1
0
0
0
0
0
0
0
0
0
0
00
2
3
4
5
6
3.45–3.46 (1H, m)
3.43–3.45 (1H, m)
3.40–3.42 (1H, m)
3.38–3.40 (1H, m)
3.71 (1H, dd, 12.0, 5.0 Hz)
2
3
4
5
00
78.4
71.6
79.0
63.1
79.1
71.6
77.3
62.7
00
00
00
6
3.89 (1H, d, 12.0 Hz)
(232 g) was fractionated via silica gel CC,
eluting with CHCl :MeOH (3:1, v/v), to
parative HPLC (YMC-ODS-A 5 mM,
250 mm £ 20 mm, detection at 210 nm)
3
give 19 major fractions A –A on the
1 19
using 15% CH CN–H O (7 ml/min) as
3 2
basis of TLC analysis. Fraction A11
16.6 g) was subjected to silica gel CC
and eluted with CHCl :MeOH (15:1 to
mobile phase to yield 3 (6.7 mg, t
R
(
102 min).
3
1
:1, v/v) to afford 12 fractions (A11-1–A11-
12). Fraction A11-8 (2 g) was separated by
0
3.3.1 (2S)-5,7,4 -Trihydroxyflavan-7-O-
b-D-glucopyranoside (1)
ODS CC (50 mM, 10–100% MeOH–
H O) to give 20 subfractions. Subfraction
2
C H O , white amorphous powder;
9
2
1
24
0
2
1
2 (184 mg) was further separated by
preparative HPLC (YMC-ODS-A 5 mM,
50 mm £ 20 mm, detection at 210 nm)
using 13% CH CN–H O (7 ml/min) as
[
(
a ] 250.0 (c 0.04, MeOH); UV
MeOH) lmax: 271 nm; CD (MeOH)
D
1
2
D1277 nm 20.552; for
(600 MHz, CD OD) and
H
NMR
C NMR
1
3
3
2
3
mobile phase to yield 1 (5.4 mg, tR
11 min) and 2 (6.2 mg, tR 121 min).
Fraction A14 (6 g) was separated by ODS
(150 MHz, CD OD) spectral data, see
3
1
Table 1; positive ESI-MS m/z: 421
þ
2
[M þ H] ; negative ESI-MS m/z: 419
CC (50 mM, 10–100%, MeOH–H O) to
2
[M 2 H] ; HR-TOF-MS m/z: 421.1496
þ
afford 10 subfractions. Subfraction A14-4
(120 mg) was further separated by pre-
[M þ H]
(calcd for C H O ,
21 25 9
421.1493).

1
254
R.-J. Zhong et al.
0
3.3.2 (2S)-5,7,4 -Trihydroxyflavan-5-O-
b-D-glucopyranoside (2)
3.4 Determination of absolute
configurations of the sugar moieties in 1–3
C H O , white amorphous powder;
2
Based on the reported procedure [10], each
2 mg of compounds 1–3 was dissolved in
1
24
0
9
2
[
(
a ]
223.0 (c 0.1, MeOH); UV
MeOH) lmax: 272 nm; CD (MeOH)
D
2 M HCl (dioxane:H O, 1:1 v/v) and
2
1
D1276 nm 21.69; for H NMR (600 MHz,
3
refluxed for 10 h. After removal of the
HCl by evaporation and extraction with
EtOAc, the H O extract was again
1
CD OD) and
C NMR (150 MHz,
CD OD) spectral data, see Table 1;
3
3
2
þ
2
positive ESI-MS m/z: 421 [M þ Na] ;
evaporated and dried in vacuo to furnish
a monosaccharide residue. The residue
was dissolved in pyridine (1 ml) to which
2 mg of L-cysteine methyl ester hydro-
chloride was added. The mixture was kept
negative ESI-MS m/z: 419 [M 2 H] ;
2
HR-TOF-MS m/z: 419.1311 [M 2 H]
(calcd for C H O , 419.1323).
21 23 9
at 608C for 2 h, evaporated under an N2
0
.3.3 (7S,8S)-3-Methoxyl-3 -O-b-D-
3
glucopyrannosyl-4 :8,5 :7-
stream, and dried in vacuo, then trimethyl-
silylated with N-trimethylsilylimidazole
0
0
0
diepoxyneolignan-4,9 -diol (3)
(0.2 ml) for 2 h. The mixture was parti-
tioned between n-hexane and H O (2 ml
C H O , white amorphous powder;
32 12
2
5
2
2
D
0
[
(
a ] 228.6 (c 0.22, MeOH); UV
MeOH) lmax: 278 nm; CD (MeOH)
each), and the n-hexane extract was
analyzed by GC. In the acid hydrolysate
of 1–3, D-glucose was verified by
comparison with retention times of its
derivatives and with those of correspond-
ing control samples prepared in the same
way.
1
D1238 nm 20.369; H NMR (600MHz,
0
DMSO) d : 1.65–1.68 (2H, m, H-8 ),
H
0
2
m, H-4 ), 3.24–3.26 (2H, m, H-2 , H-5 ),
.45–2.48 (2H, m, H-7 ), 3.16–3.19 (1H,
00
0
0
00
00
3
.27–3.30 (1H, m, H-3 ), 3.33 (1H, dd,
J ¼ 12.0, 4.2 Hz, H-9a), 3.39 (2H, t,
0
0
J ¼ 6.6 Hz, H-9 a, H-9 b), 3.47 (1H, dd,
00
J ¼ 12.0, 6.6 Hz, H-6 a), 3.54 (1H, dd,
J ¼ 12.0, 4.2 Hz, H-9b), 3.65 (1H, d,
Acknowledgments
We thank Prof. A.H. Liu at Center of Analysis
and Testing Nanchang University for NMR
measurements.
00
J ¼ 12.0 Hz, H-6 b), 3.77 (3H, s, 3-
OCH ), 4.04–4.07 (1H, m, H-8), 4.87
3
(
1H, d, J ¼ 7.2 Hz, H-7), 4.94 (1H, d,
00
J ¼ 7.2 Hz, H-1 ), 6.39 (1H, d, J ¼ 1.8 Hz,
0
0
References
H-6 ), 6.55 (1H, d, J ¼ 1.8 Hz, H-2 ), 6.79
1H, d, J ¼ 7.8 Hz, H-5), 6.82 (1H, dd,
J ¼ 7.8, 3.6 Hz, H-6), 6.98 (1H, d,
[
1] J. Yu, S.S. Liu, and L.J. Xuan, Nat. Prod.
Res. 26, 630 (2012).
(
[
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