Dimeric prenylated C6-C3 compounds from the stem bark of Illicium oligandrum

Article abstract of DOI:10.1021/np100651n

Three new dimeric prenylated C₆-C₃ compounds, namely, illicidiones A (1), B (2), and C (3), were isolated from the stem bark of Illicium oligandrum. The structure and absolute configuration of these compounds were determined by extensive spectroscopic and chemical analyses, including NMR, modified Mosher method, and single-crystal X-ray study. Compounds 1-3 exhibited weak anti-inflammatory activities. (Chemical Equation Presented).

Full text of DOI:10.1021/np100651n

NOTE
pubs.acs.org/jnp
Dimeric Prenylated C6ꢀC3 Compounds from the Stem Bark of Illicium
oligandrum
Wen-Zhao Tang,† Shuang-Gang Ma,† Jing Qu, Shi-Shan Yu,* Yun-Bao Liu, Dong-Min Su, and Jing Liu
Key Laboratory of Bioactive Substance and Resources Utilization of Chinese Herbal Medicine, Ministry of Education, Institute of
Materia Medica, Chinese Academy of Medical Sciences and Peking Union Medical College, No. 1 Xian nong tan Street, 100050,
Beijing, People’s Republic of China
S Supporting Information
b
ABSTRACT: Three new dimeric prenylated C6ꢀC3 com-
pounds, namely, illicidiones A (1), B (2), and C (3), were
isolated from the stem bark of Illicium oligandrum. The structure
and absolute configuration of these compounds were deter-
mined by extensive spectroscopic and chemical analyses, in-
cluding NMR, modified Mosher method, and single-crystal
X-ray study. Compounds 1ꢀ3 exhibited weak anti-inflamma-
tory activities.
renylated C6ꢀC3 compounds, also known as phytoqui-
noids, are characteristic constituents of the genus Illicium
(m/z 523.2299 [M þ Na]þ, calcd for C28H36O8Na 523.2308),
13C NMR, and various DEPT data. IR absorptions revealed the
presence of hydroxy (3524 and 3258 cmꢀ1), unconjugated
carbonyl (1733 cmꢀ1), R,β-conjugated carbonyl (1672,
1642 cmꢀ1), and olefinic bond (1619 cmꢀ1) groups. The 13C
NMR spectrum showed 28 carbon resonances, which were
categorized through DEPT experiments as two carbonyl, eight
quaternary, eight methine, six methylene, and four methyl
P
(Magnoliaceae).1ꢀ3 The skeletal structure of these compounds
includes a saturated or an unsaturated cyclohexanone with an
allyl group and an oxygenated prenyl group at C-2 and C-4,
respectively. In some cases, the prenyl group forms a furanoid
ring at C-5. From a chemical point of view, prenylated C6ꢀC3
compounds contain the structural units of a lignan [C6 þ C3]
and an isoprene [C5]. Some prenylated C6ꢀC3 compounds
possess activities for cancer chemoprevention.4,5
1
1
1
carbons. The H NMR, Hꢀ H COSY, and HMBC spectra
indicated the presence of four hydroxy groups that could be
exchanged by D2O, four methyl groups, two allyl groups, and two
partial structural fragments with ABX spin patterns
[C(10)H2ꢀC(11)H and C(100)H2ꢀC(110)H]. These charac-
teristic NMR data indicated that compound 1 was a prenylated
C6ꢀC3 dimer9 comprising moieties A and B (Figure 1).
Illicium oligandrum, a toxic shrub of this genus, is used in folk
medicine for treating rheumatoid arthritis. Several new rearranged
prenylated C6ꢀC3 compounds, sesquiterpenes, lignans and phenolic
diglycosides were isolated from this plant.6ꢀ8 As a result of our
continued search for the bioactive constituents of this plant, three
new dimers, illicidiones A (1), B (2), and C (3), were isolated
from the CHCl3 extract of the stem bark of I. oligandrum. This
study is the first report of prenylated C6ꢀC3 dimers. Herein, we
report the isolation, structural elucidation, and anti-inflammatory
activity for compounds 1ꢀ3.
NMR characteristics of moiety A were similar to those of 2,3-
dehydroillifunone C.9 Significant 13C NMR differences between
moiety A and 2,3-dehydroillifunone C were the upfield shifts of
C-2, C-3, and C-4 (Δδ 58.5, 95.1, and 20.1), implying the
presence of OH-2 and disappearance of an olefinic bond in
moiety A. For moiety B, compared with C-12 (δ 70.5) in moiety
A, C-120 was downfield shifted by Δδ 8.6, which suggested that
C-120 was attached to C-50 via an oxygen atom to form a
dihydropyrano ring.10 This ring with an olefinic bond at C-40
and C-50 was further confirmed by four-bond HMBCs of CH3-
130/C-50 and H2-100/C-40, 50. An exchangeable doublet at δ 4.15
Compounds 1ꢀ3 displayed several common spectroscopic
characteristics. The UV and IR spectra showed absorptions of
conjugated carbonyl and hydroxy groups. NMR analysis showed
distinctive features of prenylated C6ꢀC3 compounds isolated
from some plants of the genus Illicium.
1
1
(OH-110) and Hꢀ H COSY correlations of H-100/H-110/H
(OH-110) were observed, indicating the presence of a partial
structural fragment of C(100)H2ꢀC(110)HꢀOH in moiety B. The
linkages between moieties Aand Bfrom C-3 to C-30 and C-4 to C-60
were verified by the HMBCs of H-3/C-20, 30, 40, H-30/C-2, 3, 4, and
Illicidione A (1) was obtained as colorless prisms (MeOH).
Its molecular formula, C28H36O8, was established by HRESIMS
Received: September 15, 2010
Published: April 27, 2011
r
Copyright
2011 American Chemical Society and
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dx.doi.org/10.1021/np100651n J. Nat. Prod. 2011, 74, 1268–1271
American Society of Pharmacognosy
|

Journal of Natural Products
NOTE
Figure 4. 1H NMR chemical shift differences of the MTPA ester
derivatives of 1.
Figure 1. Structures of moieties A and B in 1.
moiety confirms the 4R absolute configuration.13,14 Using a
modified Mosher method,15 the absolute configuration of C-110
was determined as R, on the basis of the analysis of the diagnostic
proton chemical shift values between protons of the (S)- and (R)-
MTPA esters of 1 (1b and 1a) (Figure 4). Thus, compound 1,
named illicidione A, was determined to possess the 2R, 3R, 4R,
11S, 20R, 30R, 60S, 110R absolute configuration.
Illicidione B (2) was obtained as a white powder. Its molecular
formula was established as C29H36O8 from HRESIMS, 13C
Figure 2. HMBC correlations (a) and NOEs (b) of 1.
1
NMR, and various DEPT data. The H and 13C NMR spectra
showed an additional methylene resonance in the upfield (δ
3.23; δ 17.5) region compared to the spectra of 2,3-dehydroilli-
funone C and distinctive features of 2,3-dehydroillifunone C
except that C-6 was transformed to a quaternary olefinic carbon.9
Therefore, the MS and NMR data revealed that 2 was a dimeric
prenylated C6ꢀC3 compound connected by a methylene group.
The connection C-6ꢀCH2ꢀC-60 was further confirmed by the
HMBCs between H2-15 (δ 3.23) and C-1, 10 (δ 187.5), C-5, 50
(δ 175.8), and C-6, 60 (δ 108.6). The [R]20D value and the CD
spectrum of 2 were similar to those of 2,3-dehydroillifunone C
(see Supporting Information). Thus, the two monomeric moieties
in 2 were identical.
Illicidione C (3) was obtained as a white powder. Its molecular
formula was determined as C29H40O8 from HRESIMS and 13
C
NMR data. The H and 13C NMR spectra of 3, like those of
compound 2, showed signals for an additional methylene group
in the upfield (δ 3.15; δ 17.3) region and a C-6-substituted
illifunone D.1 Thus, compound 3 was also a prenylated C6ꢀC3
dimer and supported by the same HMBCs of H2-15/C-1, 10, 5, 50,
6, 60. The [R]20D value and the CD spectrum of 3 were similar to
those of illifunone D (see Supporting Information). Therefore,
compound 3 was identified as an illifunone D dimer connected
by a methylene group at C-6, 60.
1
Figure 3. ORTEP drawing of 1.
H-60/C-3, 4, 5, 10 (Figure 2) and a strong vicinal coupling 1Hꢀ H
1
COSY correlation of H-3/H-30.
The anti-inflammatory effects of 1, 2, and 3 were determined.
Compounds 1ꢀ3 were assessed by measuring the inhibitory ratios
of β-glucuronidase release in rat polymorphonuclear leukocytes
(PMNS) induced by the platelet-activating factor (PAF) in vitro.16
The inhibitory ratios of 1ꢀ3 were 38.2%, 18.6%, and 25.3% at a
concentration of 10 μM, respectively. Ginkgolide B was used as a
positive control, with an inhibitory ratio of 83.5% at 10 μM.
The stereochemistry of 1 was elucidated on the basis of NOE
correlations (Figure 2), CD data, single-crystal X-ray diffraction
analysis, and a modified Mosher method. Irradiation of H-3 (δ
2.95) showed an NOE association of OH-20 (δ 4.56) to indicate
the β-orientation of OH-20. The NOE association between OH-2
(δ 4.19) and H-30 (δ 3.14) indicated the R-orientation of OH-2.
Additionally, the R-orientation of H-11 was suggested by the NOE
association between H-11 (δ 4.66) and H-60 (δ 2.83). These
results were comfirmed by single-crystal X-ray diffraction analysis
of 1 (Figure 3). The absolute configuration could be established by
CD analysis. As in bicyclo[2,2,2]oct-5-en-2-one, the orientation of
the β,γ-unsaturated carbonyl moiety determines the sign of the
Cotton effect.11 The CD spectrum of 1 shows a negative Cotton
effect at 304 nm for the n f π* transition of the β,γ-unsaturated
carbonyl moiety, which is identical to that of bacchopetiolone.12
Therefore, C-20 possesses the R absolute configuration. Combined
with the relative configuration, the absolute configurations for
C-30, C-60, C-2, C-3, C-4, and C-11 were assigned as R, S, R, R, R,
and S, respectively. In addition, the positive Cotton effect at
253 nm for the π f π* transition of the R,β-unsaturated carbonyl
’ EXPERIMENTAL SECTION
General Experimental Procedures. Melting points were deter-
mined on an XT-4 micro melting point apparatus (uncorrected). Optical
rotations were measured on a Perkin-Elmer 341 digital polarimeter at
589 nm. UV spectra were recorded on a Hitachi UV-240 spectro-
photometer. CD analysis was performed on a JASCO J-810 spectro-
polarimeter with a 0.1 cm cell at room temperature under the following
conditions: speed 200 nm/min, time constant 1 s, and bandwidth
2.0 nm. IR spectra were recorded on KBr disks using a Nicolet Impact
410 FT-IR spectrophotometer. NMR spectra were obtained on an Inova
400 MHz spectrometer. The HSQC and HMBC experiments were
optimized for 140.0 and 8.0 Hz, respectively. ESIMS were measured on
1269
dx.doi.org/10.1021/np100651n |J. Nat. Prod. 2011, 74, 1268–1271

Journal of Natural Products
NOTE
1
1
Table 1. H (400 MHz) and 13C (100 MHz) NMR Data of
Table 2. H (400 MHz) and 13C (100 MHz) NMR Data of 2
Compound 1 (acetone-d6)
and 3 (acetone-d6)
position δC
δH (J in Hz)
position δC
δH (J in Hz)
2
3
1
2
3
4
5
6
7
198.9
77.1
44.1 2.95 (d, 2.8)
52.9
10
20
30
40
50
60
70
206.6
75.1
44.7 3.14 (d, 2.8)
108.6
position
δC
δH (J in Hz)
δC
δH (J in Hz)
1
2
3
187.5
138.8
137.0
200.4
44.7
34.6
2.23 (m)
177.1
145.5
96.6 5.28 (s)
49.9 2.22 (d, 7.2)
2.22 (d, 7.2)
133.6 5.61 (m)
118.4 4.97 (d, 12.0)
4.96 (d, 14.8)
35.3 2.33 (dd, 12.8, 10.4) 100
2.13 (dd, 10.4, 5.6)
90.2 4.66 (dd, 10.4, 5.6) 110
60.1 2.83 (s)
41.4 2.57 (dd, 14.4, 5.6)
2.23 (dd, 14.4, 8.8)
134.2 5.98 (m)
118.9 5.14 (d, 9.6)
5.10 (d, 16.4)
30.6 2.14 (dd, 16.4, 2.0)
1.88 (dd, 16.4, 7.6)
69.4 3.43
(ddd, 7.6, 5.2, 2.0)
79.1
25.7 1.14 (s)
20.5 1.05 (s)
4.56 (s)
6.57 (s)
1.83 (dd, 16.4, 9.2)
2.31 (d, 16.4)
80
90
4
5
6
7
8
9
73.0
175.8
108.6
34.1
76.7
175.8
110.0
38.7
8
9
10
11
2.87 (2 H, d, 6.8)
5.75 (m)
2.46 (m); 2.66 (m)
5.83 (m)
136.4
116.8
138.6
116.6
5.00 (d, 16.0)
5.04 (d, 16.4)
5.00 (d, 9.2)
12
13
14
2-OH
12-OH
70.5
120
4.94 (d, 9.2)
26.6 1.33 (s)
26.3 1.15 (s)
4.19 (s)
130
10
36.3
2.20 (dd, 12.4, 4.8)
2.08 (dd, 12.4, 9.6)
4.86 (dd, 9.6, 4.8)
40.7
2.29 (m)
140
20-OH
110-OH
2.17 (dd, 12.4, 9.6)
4.74 (dd, 9.6, 5.2)
3.89 (s)
4.15 (d, 5.2)
11
92.5
70.3
28.0
24.6
17.4
91.2
70.1
28.2
24.6
17.3
12
13
1.51 (s)
1.48 (s)
an Agilent 1100 Series LC/MSD trap mass spectrometer. HRESIMS
values were measured on a Bruker FTMS APEXIII 7.0T mass spectro-
meter. Column chromatography was performed on silica gel (200ꢀ300
mesh, Qingdao Marine Chemical Factory, China), ODS (40ꢀ70 μm,
Merck), and Sephadex LH-20 (Amersham Pharmacia Biotech AB,
Sweden). HPLC was carried out on a Shimadzu LC-6AD with an
SPD-10A detector. A reversed-phase C18 column (YMC Pack ODS-A
20 ꢁ 250 mm, 10 μm) and TLC with glass precoated silica gel GF254
plates (Qingdao Marine Chemical Factory, China) were employed.
Spots were visualized under UV light or by spraying with 10% H2SO4 in
95% EtOH, followed by heating.
Plant Material. The stem bark of Illicium oligandrum was collected
from Guangxi Province, China, in September 2004 and identified by
Prof. Song-ji Wei of Guangxi Traditional Medical College. A voucher
specimen (No. 04086) was deposited in the herbarium of the Institute of
Materia Medica, Chinese Academy of Medical Sciences and Peking
Union Medical College.
Extraction and Isolation. The air-dried stem bark of I. oligandrum
(3.0 kg) was extracted under reflux with 95% aqueous EtOH. The
residue (540 g) obtained by concentrating the EtOH extract in vacuo
was suspended in H2O, then partitioned successively with petroleum
ether, CHCl3, EtOAc, and n-BuOH. The CHCl3 extract (70 g) was
chromatographed on a silica gel column eluted with petroleum
etherꢀMe2CO (40:1 to 1:1 gradient) to yield fractions A1ꢀA6. Fraction
A5 (7.2 g) was again chromatographed over a silica gel column with
petroleum etherꢀMe2CO (10:1, 5:1, 3:1, and 1:1, v/v) to give fractions
D1ꢀD5. Fraction D3 (1.8 g) was separated by an RP C18 column
(aqueous MeOH, 40%) to yield 1 (70 mg). Fraction D2 (2.5 g) was
14
1.07 (s)
1.04 (s)
15
3.23 (2H, s)
4.70 (s)
3.15 (2H, s)
4.52 (s)
4-OH
12-OH
4.43 (s)
4.44 (s)
Esterification of 1. A 16 μL portion of (S)-MTPACl was added to
a solution of 1 (8.6 mg) in pyridine (0.5 mL), and the mixture was kept at
room temperature for 2 h. The reaction mixture was diluted with EtOH,
evaporated, and purified by preparative silica gel TLC developed with
n-hexaneꢀEt2O (9:1) to afford the (R)-MTPA ester 1a (3.2 mg). In the
same manner, compound 1 (9.8 mg) was treated with (R)-MTPACl to
give the (S)-MTPA ester 1b (3.6 mg).
(R)-MTPA ester (1a): 1H NMR (500 MHz, acetone-d6) δ 7.49ꢀ7.44
(5H, m, aromatic), 5.84 (1H, m, H-80), 5.62 (1H, m, H-8), 5.31 (1H, s,
H-6), 5.02 (1H, t, J = 5.0 Hz, H-110), 5.00 (1H, d, J = 8.0 Hz, H-90a), 4.97
(1H, d, J = 13.0 Hz, H-90b), 4.73ꢀ4.67 (2H, m, H2-9), 4.55, 4.27, 3.90
(each 1H, s, OH ꢁ 3), 3.46 (3H, s, OCH3 of MTPA), 3.14 (1H, d, J = 2.5
Hz, H-30), 2.99 (1H, d, J = 2.5 Hz, H-3), 2.91 (1H, s, H-60), 2.47 (1H, dd,
J = 18.0, 5.0 Hz, H-100R), 1.91 (1H, dd, J = 18.0, 5.0 Hz, H-100β), 2.35
(1H, dd, J = 13.0, 10.5 Hz, H-10R), 2.15 (1H, dd, J = 13.0, 5.5 Hz,
H-10β), 2.45 (1H, dd, J = 16.5, 5.5 Hz, H-70a), 2.00 (1H, dd, J = 16.5, 9.5
Hz, H-70b), 2.23 (2H, d, J = 7.0 Hz, H2-7), 1.35 (3H, s, CH3-13), 1.14
(3H, s, CH3-14), 1.20 (3H, s, CH3-130), 1.13 (3H, s, CH3-140); ESIMS
(positive) m/z 717.2 [M þ H]þ, 739.2 [M þ Na]þ.
1
(S)-MTPA ester (1b): H NMR (500 MHz, acetone-d6) δ 7.52ꢀ7.47
(5H, m, aromatic), 5.99 (1H, m, H-80), 5.63 (1H, m, H-8), 5.32 (1H, s,
H-6), 5.14 (1H, d, J = 10.5 Hz, H-90a), 5.09 (1H, d, J = 17.0 Hz, H-90b),
5.01 (1H, m, H-110), 5.00ꢀ4.97 (2H, m, H2-9), 4.67 (1H, dd, J = 10.5, 5.5
Hz, H-11), 4.64, 4.30, 3.90 (each 1H, s, OH ꢁ 3), 3.43 (3H, s, OCH3 of
MTPA), 3.22 (1H, d, J = 2.5 Hz, H-30), 3.02 (1H, d, J = 2.5 Hz, H-3), 2.89
(1H, s, H-60), 2.55 (1H, dd, J = 17.0, 5.5 Hz, H-100R), 2.13 (1H, dd,
J = 17.0, 5.5 Hz, H-100β), 2.36 (1H, dd, J = 12.5, 10.0 Hz, H-10R), 2.17
(1H, m, H-10β), 2.59 (1H, dd, J = 14.5, 5.5 Hz, H-70a), 2.16 (1H, m,
H-70b), 2.24 (2H, d, J = 7.0 Hz, H2-7), 1.35 (3H, s, CH3-13), 1.15 (3H, s,
CH3-14), 1.09 (3H, s, CH3-130), 1.02 (3H, s, CH3-140); ESIMS (positive)
m/z 717.2 [M þ H]þ.
separated on
a silica gel column repeatedly with petroleum
etherꢀEtOAc (20:1, 10:1, 5:1, 3:1, and 1:1, v/v) to give fractions
E1ꢀE6. Fraction E2 (125 mg) was purified by RP-HPLC with
MeOHꢀH2O (60:40) as mobile phase to yield 2 (47 mg). Compound
3 (41 mg) was obtained from fraction E3 (118 mg) by RP-HPLC with
MeOHꢀH2O (58:42) as mobile phase.
Illicidione A (1): colorless prism; mp 213ꢀ215 °C; [R]20D þ36.5 (c
0.5, MeOH); UV (MeOH) (log ε) λmax 265 (4.26) nm; CD (MeOH)
λmax (mdeg) 253 (þ20), 304 (ꢀ16.2) nm; IR (KBr) νmax 3524, 3258,
2978, 1733, 1672, 1642, 1619, 1414 cmꢀ1; 1H and 13C NMR data, see
Table 1; ESIMS (positive) m/z 501.2 [M þ H]þ; HRESIMS (positive)
m/z 501.2472 [M þ H]þ (calcd for C28H37O8 501.2488), 523.2299
[M þ Na]þ (calcd for C28H36O8Na 523.2308).
X-ray Structural Determination of Illicidione A (1). X-ray
diffraction intensity data of 1 were collected on an MAC DIP-2030K
1270
dx.doi.org/10.1021/np100651n |J. Nat. Prod. 2011, 74, 1268–1271

Journal of Natural Products
NOTE
diffractometer with graphite-monochromated Mo KR radiation (λ =
0.71073 Å) by the ω scan technique [scan width 0ꢀ180°, 2θ e 50°].
(8) (a) Tang, W. Z.; Ma, S. G.; Yu, S. S.; Qu, J.; Liu, Y. B.; Liu, J.
J. Nat. Prod. 2009, 72, 1017–1021. (b) Ma, S. G.; Tang, W. Z.; Liu, Y. X.;
Hu, Y. C.; Yu, S. S.; Zhang, Y.; Chen, X. G.; Qu, J.; Ren, J. H.; Liu, Y. B.;
Xu, S.; Liu, J.; Liu, Y. Y.; Li, Y.; L€u, H. N.; Wu, X. F. Phytochemistry 2011,
72, 115–125. (c) Ma, S. G.; Tang, W. Z.; Yu, S. S.; Zhang, Y.; Chen, X. G.;
Liu, Y.; Wang, W. J.; Qu, J.; Xu, S.; Ren, J. H.; Li, Y.; L€u, H. N. Carbohydr.
Res. 2011, doi:10.1016/j.carres. 2011.03.021.
(9) Fukuyama, F.; Shida, N.; Hata, Y.; Kodama, M. Phytochemistry
1994, 36, 1497–1503.
(10) Rubio, O. C.; Cuellar, A. C.; Rojas, N.; Castro, H. V.; Rastrell,
L.; Aquino, R. J. Nat. Prod. 1999, 62, 1013–1015.
(11) Kirk, D. N. Tetrahedron 1986, 42, 777–818.
(12) Zdero, C.; Bohlmann, F.; Niemeyer, H. M. Phytochemistry
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Crystal data: C28H36O8 H2O, MW 518.57, colorless prism crystals with
3
size 0.10 ꢁ 0.30 ꢁ 0.60 mm3, monoclinic, space group P21, T = 253(2) K,
a = 9.393(1) Å, b = 14.905(1) Å, c = 19.192(1) Å, V = 2686.9(4) Å3,
Dc = 1.282 g/cm3, Z = 4. 2755 reflections were collected, of which 2619
with |F|2 g 2σ|F|2 were observed. The structure was solved by direct
methods and refined by block-matrix least-squares procedure to R1 =
0.0463, wR2 = 0.1264 (w = 1/σ|F|2). Hydrogen positions were found
from difference Fourier maps and geometric calculations. All calcula-
tions were carried out on a personal computer using the SHELX-97
program system.
CCDC-759134 (for 1) contains supplementary crystallographic data.
These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/
cif.
Illicidione B (2): white powder; [R]20 ꢀ24.4 (c 0.4, MeOH); UV
(15) Ohtani, I.; Kusumi, T.; Kashman, Y.; Kikisama, H. J. Am. Chem.
Soc. 1991, 113, 4092–4096.
(16) Kang, J.; Chen, R. Y.; Yu, D. Q. Planta Med. 2006, 72, 52–59.
D
(MeOH) (log ε) λmax 242 (4.26), 315 (3.28) nm; CD (MeOH) λmax
(mdeg) 253 (ꢀ88.2), 306 (ꢀ62.0), 341 (þ58.0) nm; IR (KBr) νmax
3418, 2977, 1676, 1642, 1619, 1345, 1209 cmꢀ1; 1H and 13C NMR data,
see Table 2; ESIMS (positive) m/z 513.2 [M þ H]þ, 535.2 [M þ Na]þ;
HRESIMS (positive) m/z 535.2305 [M þ Na]þ (calcd for C29H36O8Na
535.2302).
Illicidione C (3): white powder; [R]20 þ9.4 (c 0.15, MeOH); UV
D
(MeOH) (log ε) λmax 265 (4.43) nm; CD (MeOH) λmax (mdeg) 261
(ꢀ61.4), 305 (þ41.2) nm; IR (KBr) νmax 3361, 2975, 1656, 1624, 1594,
1346, 1217, 1036, 805 cmꢀ1; 1H and 13C NMR data, see Table 2; ESIMS
(positive) m/z 539.2 [M þ Na]þ; HRESIMS (positive) m/z 517.2800
[M þ H]þ (calcd. for C29H41O8 517.2795).
Anti-inflammatory Activity Assay. On the basis of reported
procedures,16 the anti-inflammatory activities of compounds 1ꢀ3 were
assayed by measuring the inhibition of the platelet-activating factor
induced release of β-glucuronidase from rat polymorphonuclear leuko-
cytes in vitro.
’ ASSOCIATED CONTENT
S
Supporting Information. This material is available free
b
of charge via the Internet at http://pubs.acs.org.
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: yushishan@imm.ac.cn. Tel: þ86-10-63165326. Fax:
þ86-10-63017757.
Author Contributions
†These authors contributed equally to this work.
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