Four new cytotoxic tetrahydrofuranoid lignans from sinopodophyllum emodi

Article abstract of DOI:10.1055/s-0031-1298201

Four new tetrahydrofuranoid lignans, (-)-tanegool-7′-methyl ether (1), (+)-7′-methoxylariciresinol (2), sinolignan C (3), and epipinoresinol-4,4-di-Oβ- D-glucopyranoside (4), were isolated from the roots and rhizomes of Sinopodophyllum emodi together with one known lignan (5). Their structures and stereochemistry were elucidated on the basis of spectroscopic and mass spectrometric evidence. The isolation of compounds 1-5 represents the first report of tetrahydrofuran lignans from the genus Sinopodophyllum. The cytotoxic activities of all isolated compounds were evaluated against HeLa and KB cell lines, and compound 1 showed the most potent cytotoxicity with ICvalues of 9.7 μM and 4.7 μM, respectively.

Full text of DOI:10.1055/s-0031-1298201

480 Letters
Key words
tetrahydrofuranoid lignans · Sinopodophyllum emodi · Berberi-
daceae · cytotoxic activities
Four New Cytotoxic Tetra-
hydrofuranoid Lignans from
Supporting information available online at
Sinopodophyllum emodi
http://www.thieme-connect.de/ejournals/toc/plantamedica
Yan-Jun Sun1,2,3, Zhan-Lin Li1,2, Hong Chen4,5, Xiao-Qiu Liu2,
Wei Zhou1,2, Hui-Ming Hua1,2
Sinopodophyllum emodi (Wall.) Ying (Berberidaceae) is distrib-
uted widely in the southwest of China [1]. The dried roots and
rhizomes of S. emodi, called “Taoerqi” in Chinese, are used as a
folk medicine for the treatment of certain cancers, various verru-
coses [1], as a cathartic and anthelminthic [2], as well as against
rheumatoid ache [3] and pyogenic infection of the skin tissue [4].
Previous chemical and pharmacological investigations on S. emo-
di revealed the presence of bioactive aryltetralin lignans [1,5–7],
and cytotoxic and antiviral properties [4,7]. In a continuation of
our search for cytotoxic natural products, five tetrahydrofuranoid
1
Key Laboratory of Structure-Based Drug Design & Discovery,
Ministry of Education, Shenyang Pharmaceutical University,
Shenyang, PR China
School of Traditional Chinese Materia Medica, Shenyang
2
Pharmaceutical University, Shenyang, PR China
School of Pharmacy, Henan College of Traditional Chinese
3
Medicine, Zhengzhou, PR China
Tianjin Key Laboratory for Biomarkers of Occupational and
4
Environmental Hazard, Tianjin, PR China
Pharmacognosy Division, Medical College of Chinese
5
"
lignans (l Fig. 1) were obtained. We herein described the isola-
Peopleʼs Armed Police Force, Tianjin, PR China
tion and structure elucidation of four new lignans (1–4) and the
evaluation of the cytotoxic activity of all isolated compounds,
along with their preliminary structure–activity relationships.
Compound 5 was identified as lanicepside A by comparison with
the literature [8].
Abstract
!
Four new tetrahydrofuranoid lignans, (−)-tanegool-7′-methyl
ether (1), (+)-7′-methoxylariciresinol (2), sinolignan C (3), and
epipinoresinol-4,4′-di-O-β-D-glucopyranoside (4), were isolated
from the roots and rhizomes of Sinopodophyllum emodi together
with one known lignan (5). Their structures and stereochemistry
were elucidated on the basis of spectroscopic and mass spectro-
metric evidence. The isolation of compounds 1–5 represents the
first report of tetrahydrofuran lignans from the genus Sinopodo-
phyllum. The cytotoxic activities of all isolated compounds were
evaluated against HeLa and KB cell lines, and compound 1
showed the most potent cytotoxicity with IC50 values of 9.7 µM
and 4.7 µM, respectively.
Compound 1 was obtained as a sticky oil and possessed a molec-
ular formula C21H26O7, as revealed from its HR‑ESI‑MS analysis
1
(m/z 413.1574 [M + Na]+). The H‑NMR spectrum (l Table 1)
"
showed proton signals of two ABX systems of aromatic protons
at δH 6.83, 6.75, 6.70, 6.81, 6.70, and 6.70, two aromatic CH3O
groups at δH 3.73 (3H, s) and 3.76 (3H, s), indicating the presence
of two trisubstituted benzene rings. Six oxygenated aliphatic pro-
tons at δH 3.44, 3.49 (2H), 3.54, 3.95, and 4.51, together with two
aliphatic protons at δH 2.07 and 2.50 were evidence for the pres-
ence of a tetrahydrofuranoid lignan skeleton [8], which was sup-
ported by 13C‑NMR analysis. In the 13C‑NMR spectrum, apart
from the twelve aromatic and three CH3O signals, there were six
Fig. 1 Compounds 1–5 isolated from S. emodi.
Sun Y-J et al. Four New Cytotoxic… Planta Med 2012; 78: 480–484

Letters 481
Table 1 1H NMR data (300 MHz, δ in ppm, J in Hz) of compounds 1–4 in DMSO-d6.
No.
1
2
3
4
2
5
6
7
8
9
6.81 (1H, brs)
6.70 (1H, m)
6.70 (1H, m)
4.51 (1H, d, 7.4)
2.07 (1H, m)
3.49 (2H, m)
6.85 (1H, brs)
6.71 (1H, m)
7.02 (1H, d, 1.7)
7.06 (1H, d, 8.4)
6.90 (1H, dd, 8.4, 1.7)
4.69 (1H, d, 6.2)
2.38 (1H, m)
6.94 (1H, d, 1.8)
7.04 (1H, d, 8.4)
6.83 (1H, dd, 8.4, 1.8)
4.79 (1H, d, 5.9)
3.37 (1H, m)
6.72 (1H, m)
4.50 (1H, d, 7.1)
1.60 (1H, m)
3.05 (1H, m),
2.89 (1H, m)
3.65 (1H, m),
3.74 (1H, m),
3.49 (1H, m)
3.07 (1H, m)
2′
5′
6′
7′
8′
9′
6.83 (1H, brs)
6.75 (1H, d, 8.0)
6.70 (1H, m)
3.95 (1H, d, 8.9)
2.50 (1H, m)
3.54 (1H, m),
3.44 (1H, m)
3.73 (3H, s)
6.75 (1H, brs)
6.71 (1H, d, 8.0)
6.62 (1H, brd, 8.0)
3.90 (1H, d, 9.3)
2.41 (1H, m)
6.96 (1H, d, 1.7)
6.75 (1H, d, 8.0)
6.81 (1H, dd, 8.0, 1.7)
4.64 (1H, d, 6.5)
2.38 (1H, m)
6.95 (1H, d, 1.8)
7.03 (1H, d, 8.4)
6.86 (1H, dd, 8.4, 1.8)
4.37 (1H, d, 6.8)
2.84 (1H, m)
4.03 (1H, dd, 4.0, 8.8)
3.79 (1H, brd, 8.2)
3.73 (3H, s)
3.65 (1H, m)
4.08 (1H, m)
3.49 (1H, m)
3.75 (1H, m)
10
10′
11′
1′′
2′′
3′′
4′′
5′′
6′′
3.75 (3H, s)
3.76 (3H, s)
3.76 (3H, s)
3.76 (3H, s)
3.75 (3H, s)
3.76 (3H, s)
3.02 (3H, s)
3.05 (3H, s)
4.88 (1H, d, 7.3)
3.24 (1H, m)
3.25 (1H, m)
3.14 (1H, m)
3.28 (1H, m)
3.44 (1H, m),
3.69 (1H, m)
4.88 (1H, d, 7.1)
3.24 (1H, m)
3.26 (1H, m)
3.14 (1H, m)
3.27 (1H, m)
3.44 (1H, m),
3.66 (1H, m)
4.87 (1H, d, 7.0)
3.24 (1H, m)
3.26 (1H, m)
3.14 (1H, m)
3.27 (1H, m)
3.44 (1H, m),
3.66 (1H, m)
1′′′
2′′′
3′′′
4′′′
5′′′
6′′′
sp3 C-atoms, including two oxymethines at δC 83.3 and 85.7 and
two oxymethylenes at δC 61.5 and 69.1. The 8, 8′-linked tetrahy-
drofuran skeleton between two propanyl groups was certified by
connectivities of H-8 with H-7, H-9, and H-8′, and of H-8′ with H-
were similar with those of compound 1. The COSY, HSQC, and
HMBC spectra of 2 also showed similar cross-peaks with those
of 1. Due to apparent differences of the NOESY correlations in 1
and 2, it was reasonably assumed that 2 was a stereoisomer of 1.
The relative configuration between H-7 and H-8 was determined
as trans on the basis of H-7 at δH 4.50 [10]. The relative configu-
ration between H-8′ and H-8 was deduced as cis due to the ab-
sence of a cross-peak of H-7/H-8′ in the NOESY spectrum, which
was supported by the chemical shift of H-9 in compound 2 [13].
H-9 of compound 2 shifted upfield to δH 3.05 (1H, m) and 2.89
(1H, m) due to the influence of the 7′-OCH3, while H-9 of com-
pound 1 gave a downfield signal at δH 3.49 (2H, m). Thus, the
structure of 2 was determined as (7S*,8R*,8′R*)-3,3′,7′-trime-
thoxy-4,9,4′-trihydroxy-8.8′,7.O.9′-lignan, and named (+)-7′-me-
thoxylariciresinol.
Compound 3 was isolated as amorphous powder. Its molecular
formula was established as C26H34O12, derived from HR‑ESI‑MS
analysis (m/z 561.1945 [M + Na]+). The 1H‑NMR spectrum
showed proton signals of two aromatic CH3O groups at δH 3.75
(6H, s), two ABX systems of aromatic protons at δH 7.02 (1H, d,
J = 1.7 Hz), 6.90 (1H, dd, J = 1.7, 8.4 Hz), 7.06 (1H, d, J = 8.4 Hz),
6.96 (1H, d, J = 1.7 Hz), 6.81 (1H, dd, J = 1.7, 8.0 Hz), and 6.75 (1H,
d, J = 8.0 Hz), six oxygenated aliphatic protons at δH 3.65 (2H),
3.49 (2H), 4.64, 4.69, and two aliphatic protons at δH 2.38 (2H),
indicating the presence of a tetrahydrofuranoid lignan skeleton.
The 7.O.7′ oxygen bridge of the tetrahydrofuran ring moiety was
established based on 13C‑NMR and HMBC analyses. The 13C‑NMR
spectrum revealed four O-bearing C-atoms at δc 82.0, 81.7, 58.7,
1
7′, H-9′, and H-8 in the H-1H COSY experiment. The above data
suggested that 1 was tanegool methyl ether [9], which was sup-
ported by the HMBC spectrum. The remaining CH3O group was
located at C-7′, based on the HMBC correlation between CH3O
group protons at δH 3.02 (3H, s) and C-7′ (δC 85.7). The relative
configuration in the tetrahydrofuran ring was determined by
the H-7 chemical shift and NOESY experiment. For a cis-orienta-
tion of substituents at C-7 and C-8, the signal of H-7 was at around
5.5 ppm, while for a trans-orientation, the signal of H-7 upfield
shifted to around 4.7 ppm [10]. According to a signal of H-7 at δH
4.51, the orientation of H-7/H-8 of compound 1 was determined
to be trans. All trans orientation of H-7/H-8/H-8′ was determined
by the cross-peak of H-7/H-9, H-7/H-8′, H-8/H-7′, H-9/H-8′ in the
NOESY spectrum. There were no definitive conclusions on the re-
lationships between the absolute configuration and circular di-
chroism (CD) in this series of tetrahydrofuranoid lignans [11,
12]. Although the CD spectrum of 1 showed the positive absorp-
tion peaks at 228 and 284 nm, the absolute configuration was not
determined. Thus, the structure of
1 was determined as
(7S*,8R*,8′S*)-3,3′,7′-trimethoxy-4,9,4′-trihydroxy-8.8′,7.O.9′-lig-
nan and named (−)-tanegool-7′-methyl ether.
Compound 2 was obtained as a sticky oil and possessed a molec-
ular formula of C21H26O7, derived from its HR‑ESI‑MS analysis
(m/z 413.1562 [M + Na]+). The 1H‑NMR and 13C‑NMR data of 2
Sun Y-J et al. Four New Cytotoxic… Planta Med 2012; 78: 480–484

482 Letters
Table 2 13C NMR data (75 MHz, δ
in ppm) of compounds 1–4 in
DMSO-d6.
No.
1
2
3
4
1
2
133.6 (s)
110.4 (d)
147.5 (s)
145.7 (s)
115.1 (d)
118.8 (d)
83.3 (d)
53.8 (d)
61.5 (t)
133.6 (s)
110.4 (d)
147.5 (s)
145.7 (s)
115.2 (d)
118.7 (d)
82.7 (d)
52.2 (d)
60.4 (t)
136.7 (s)
110.8 (d)
148.9 (s)
145.8 (s)
115.2 (d)
118.5 (d)
81.7 (d)
51.4 (d)
58.7 (t)
132.5 (s)
110.0 (d)
148.7 (s)
145.5 (s)
114.9 (d)
117.7 (d)
81.9 (d)
49.4 (d)
69.1 (t)
3
4
5
6
7
8
9
10
1′
55.6 (q)
131.3 (s)
111.0 (d)
147.7 (s)
146.3 (s)
115.2 (d)
120.4 (d)
85.7 (d)
48.3 (d)
69.1 (t)
55.6 (q)
130.9 (s)
111.0 (d)
147.7 (s)
146.2 (s)
115.2 (d)
120.5 (d)
85.4 (d)
48.0 (d)
70.4 (t)
55.6 (q)
133.5 (s)
110.7 (d)
147.5 (s)
145.9 (s)
115.2 (d)
118.9 (d)
82.0 (d)
51.2 (d)
58.6 (t)
55.7 (q)
135.3 (s)
110.5 (d)
149.0 (s)
146.0 (s)
115.3 (d)
118.2 (d)
86.7 (d)
54.1 (d)
70.4 (t)
2′
3′
4′
5′
6′
7′
8′
9′
10′
11′
1′′
2′′
3′′
4′′
5′′
6′′
1′′′
2′′′
3′′′
4′′′
5′′′
6′′′
55.7 (q)
55.8 (q)
55.7 (q)
55.8 (q)
55.6 (q)
55.7 (q)
100.2 (d)
73.3 (d)
76.9 (d)
69.7 (d)
77.1 (d)
60.8 (t)
100.2 (d)
73.3 (d)
77.0 (d)
69.8 (d)
77.1 (d)
60.8 (t)
100.2 (d)
73.3 (d)
77.0 (d)
69.8 (d)
77.1 (d)
60.8 (t)
and 58.6, which were characteristic of a 7.O.7′-tetrahydrofura-
noid lignan. In the HMBC spectrum, the cross-peaks of H-7 at δH
4.69 (δC 81.7) with C-9 (δC 58.7), C-7′ (δC 82.0), C-8′ (δC 51.2), and
of H-7′ at δH 4.64 (δC 82.0) with C-9′ (δC 58.6), C-7 (δC 81.7), C-8 (δC
51.4) further supported the proposed structure. Two characteris-
tic downfield CH groups at δH 4.69 (1H, d, J = 6.2 Hz), 4.64 (1H, d,
J = 6.5 Hz) and six characteristic aliphatic C-atom signals at δC 81.7
(CH), 51.4 (CH), 58.7 (CH2), 82.0 (CH), 51.2 (CH), and 58.6 (CH2)
suggested that the planar structure of the aglycone of compound
3 was the same as (+)-neo-olivil [14]. The chemical shifts of H-7
(δH 4.69) and H-7′ (δH 4.64) indicated that each HOCH2 group was
situated in a trans-relation to the vicinal aryl group [15]. The con-
figuration of the aglycone was thus concluded to be either the all
trans form or the meso form. The cis-orientation between H-7
and H-7′ was determined by the cross-peak of H-7/H-7′ in the
NOESY spectrum. Furthermore, compound 3 showed no Cotton
effect (220–350 nm), but known compounds with all trans-con-
figuration did so in CD spectra [16,17]. Thus, the configuration
for 3 was the meso form. The presence of a β-glucopyranosyl moi-
ety in the molecule was indicated by the carbon signals at δC
100.2, 73.3, 76.9, 69.7, 77.1, 60.8 and an anomeric proton signal
at δH 4.88 (1H, d, J = 7.3 Hz). On acid hydrolysis, 3 afforded D-glu-
cose. The anomeric proton at δH 4.88 showed a long range cor-
relation with the aromatic carbon signals at δC 145.8 which was
assigned to the C-4. On the basis of the above evidences, the
structure of 3 was determined as (7R*,8S*,8′R*,7′S*)-3,3′-di-
methoxy-9,4′,9′-trihydroxy-8.8′,7.O.7′-lignan-4-O-β-D-glucoside
and named sinolignan C.
Compound 4 was obtained as amorphous powder. Its molecular
formula was established as C32H42O16 by HR‑ESI‑MS analysis
(m/z 705.2370 [M + Na]+). The 1H‑NMR and 13C‑NMR signals were
1
1
"
assigned by the H- H COSY, HSQC, and HMBC analysis (l Tables
1 and 2), indicating the presence of two guaiacyl and two gluco-
syl groups. Two characteristic downfield CH signals at δH 4.79
(1H, d, J = 5.9 Hz), 4.37 (1H, d, J = 6.8 Hz) and six characteristic ali-
phatic carbon signals at δC 81.9 (CH), 49.4 (CH), 69.1 (CH2), 86.7
(CH), 54.1 (CH), and 70.4 (CH2) suggested that compound 4 was
a ditetrahydrofuranoid lignan. The 8, 8′-linkage was certified by
connectivities of H-8 with H-7, H-9, and H-8′, and of H-8′ with
1
H-7′, H-9′, and H-8 in the H-1H COSY experiment. In the HMBC
spectrum, the cross-peaks of H-7 at δH 4.79 (δC 81.9) with C-9
(δC 69.1), C-8′ (δC 54.1), and C-9′ (δC 70.4) and of H-7′ at δH 4.37
(δC 86.7) with C-9′ (δC 70.4), C-8 (δC 49.4), and C-9 (δC 69.1) sup-
ported 7.O.9′ and 7′.O.9 oxygen bridges in the ditetrahydrofuran
ring moiety. The relative and absolute configurations of the agly-
cone of compound 4 were determined by comparison of NMR da-
ta and CD spectrum of known analogous compounds [18–21] and
the combined NOESY experiment. Due to an epi-diepoxy system
in compound 4, the signals for the benzylic protons H-7 and H-7′
were not identical and appeared as doublets at δH 4.79 (1H, d,
J = 5.9 Hz) and 4.37 (1H, d, J = 6.8 Hz), respectively [19]. The 13C
NMR spectrum was important in establishing the orientation of
the aryl groups. For an equatorial guaiacyl group, C-1 appeared
in downfield at around δC 133.0 in CDCl3, while for an axial
guaiacyl group in upfield at around δC 130.6 [18–20]. Thus, con-
sidering the solvent effect and glycosidation shift on the aryl
Sun Y-J et al. Four New Cytotoxic… Planta Med 2012; 78: 480–484

Letters 483
Table 3 Cytotoxic activities of compounds 1–5 against HeLa and KB cell lines.
Compound
IC50a (µM)
HeLa
Compound
IC50a (µM)
HeLa
KB
KB
1c
2c
3c
9.7 1.0
4.7 0.4
4c
5c
> 100
> 100
> 100
32.2 3.0
> 100
> 100
99.6 8.3
4.0 0.3
> 100
Etoposideb
10.0 0.9
a IC50 is defined as the concentration of drug required to inhibit cell growth by 50% compared with untreated control. It is expressed as mean SD of at least three determinations.
b Reference control (> 98%). c The purity (%) of tested compound exceeded 90%
group, values of C-1 and C-1′ at δC 135.3 and 132.5 in compound 4
accounted for the appearances of equatorial and axial guaiacyl
groups. The NOESY cross-peak was observed between H-7 (δH
4.79) and H-8′ (δH 2.84). Thus, the relative configuration could
be proposed as 7,8-cis-8,8′-cis-7′,8′-trans. The CD spectrum of
compound 4 was identical with episesartemin which has the ab-
solute configuration 7R,8R,8′R,7′S [21]. Therefore, the aglycone of
compound 4 was (+) epipinoresinol. On acid hydrolysis, 4 af-
forded D-glucose. The anomeric protons of glucoses at δH 4.88
(1H, d, J = 7.1 Hz) and 4.87 (1H, d, J = 7.0 Hz), respectively, showed
HMBC correlations with the aromatic C-atoms at C-4 (δC 145.5)
and C-4′ (δC 146.0). Accordingly, compound 4 was established as
epipinoresinol-4, 4′-di-O-β-D-glucopyranoside.
284 (+ 27.0); UV (MeOH): λmax (log ε) = 208 (2.54), 230 (1.34),
280 (0.65) nm; IR (KBr): νmax = 3419, 2936, 1607, 1517, 1274,
1157, 1121, 1083, 1032 cm−1; 1H‑NMR (300 MHz, DMSO-d6) data,
13
"
"
see l Table 1; C‑NMR (75 MHz, DMSO-d6) data, see l Table 2;
(+) ESI‑MS: m/z 413 [M + Na]+, 429 [M + K]+; (−) ESI‑MS: m/z 389
[M – H]−, 425 [M + Cl]−; HR‑ESI‑MS: m/z 413.1562 [M + Na]+
(calcd. for C21H26O7Na+, 413.1576).
Sinolignan C (3): Amorphous powder; [α]2D5 − 10.0 (c 0.3, MeOH);
CD (c = 1.6 g/L, MeOH) Δ ε (nm) no Cotton effect; UV (MeOH):
λmax (log ε) = 208 (1.82), 228 (0.50), 278 (0.16) nm; IR (KBr):
ν
max = 3410, 2928, 1619, 1520, 1271, 1221, 1095, 1043 cm−1
;
H‑NMR (300 MHz, DMSO-d6) data, see l Table 1; 13C‑NMR
1
"
"
(75 MHz, DMSO-d6) data, see l Table 2; (+) ESI‑MS: m/z 561 [M
All isolated compounds were evaluated for cytotoxic activities
against human uterine cervical adenocarcinoma (HeLa) and hu-
+ Na]+, 577 [M + K]+; (−) ESI‑MS: m/z 537 [M – H]−, 573 [M + Cl]−;
HR‑ESI‑MS: m/z 561.1945 [M + Na]+ (calcd. for C26H34O12Na+,
561.1948).
"
man oral squamous carcinoma (KB) cell lines (l Table 3). Com-
pounds 1 and 2 showed cytotoxicity and compounds 3, 4, and 5
displayed no cytotoxicity against the HeLa cell line. Compound 1
displayed cytotoxicity against the KB cell line and was more cyto-
toxic than etoposide. Compound 2 is the stereoisomer of 1, and
the variation of cytotoxicity between them indicated a critical
stereochemistry requirement. Compound 1, which is the first re-
ported example of 8.8′-trans,7.O.9′ monotetrafuran lignan exhib-
iting cytotoxicity in the KB cell line, represents a novel analogue
as an antitumor lead compound for SAR and lead optimization
studies.
Epipinoresinol-4,4′-di-O-β‑D-glucopyranoside (4): Amorphous
powder; [α]2D5 − 25.0 (c 0.3, MeOH); CD (c = 1.8 g/L, MeOH) Δ ε
(nm) 230 (+ 1.1), 238 (+ 0.8), 254 (− 1.0), 286 (+ 0.5); UV (MeOH):
λ
max (log ε) = 208 (2.46), 228 (1.10), 278 (0.36) nm; IR (KBr): νmax =
3420, 2928, 1631, 1514, 1273, 1223, 1160, 1077, 1045 cm−1
;
1
H‑NMR (300 MHz, DMSO-d6) data, see l Table 1; 13C‑NMR
"
"
(75 MHz, DMSO-d6) data, see l Table 2; (+) ESI‑MS: m/z 705 [M +
Na]+; (−) ESI‑MS: m/z 681 [M – H]−, 717 [M + Cl]−, 727 [M + HCOO]−;
HR‑ESI‑MS: m/z 705.2370 [M + Na]+ (calcd. for C32H42O16Na+,
705.2371).
Materials and Methods
Supporting information
!
General experimental procedures, detailed extraction/isolation
of compounds, NMR and CD spectra of new compounds, as well
as protocols for cell culture and cytotoxicity assays, along with
the determination of the absolute configurations of the sugar
moieties are available as Supporting Information.
The plant material, purchased from Yuntian Medicinal Material
Corporation, was cultivated in Deqin, Yunnan province, Peopleʼs
Republic of China, in September 2008, and was identified as the
roots and rhizomes of Sinopodophyllum emodi (Wall.) Ying by
Professor Qishi Sun of the Shenyang Pharmaceutical University,
according to the Chinese Traditional Medicine Dictionary [22]. A
voucher specimen (SE 20081009) was deposited in the Depart-
ment of Natural Products Chemistry, Shenyang Pharmaceutical
University, Shenyang, Peopleʼs Republic of China.
Acknowledgements
!
The authors wish to thank Professor Qishi Sun (Shenyang Phar-
maceutical University, Shenyang, Peopleʼs Republic of China) for
identification of the plant material. This work was supported by
the National Natural Science Foundation of China (No.
30873363), Program of Science Foundation of Tianjin
(08JCYBJC070000), and Major Program of Science Foundation of
Tianjin 09ZCKFSH01700).
(−)-Tanegool-7′-methyl ether (1): Sticky oil; [α]2D5 − 19.4 (c 0.14,
CHCl3); CD (c = 1.2 g/L, MeOH) Δ ε (nm) 228 (+ 54.9), 258 (− 7.6),
284 (+ 18.5); UV (MeOH): λmax (log ε) = 208 (2.73), 230 (1.82),
280 (0.81) nm; IR (KBr): νmax = 3420, 2935, 1604, 1516, 1273,
1158, 1123, 1057, 1034 cm−1; 1H‑NMR (300 MHz, DMSO-d6) data,
13
"
"
see l Table 1; C‑NMR (75 MHz, DMSO-d6) data, see l Table 2;
(+) ESI‑MS: m/z 413 [M + Na]+, 429 [M + K]+; (−) ESI‑MS: m/z 389
[M – H]−, 425 [M + Cl]−; HR‑ESI‑MS: m/z 413.1574 [M + Na]+
(calcd. for C21H26O7Na+, 413.1576).
Conflict of Interest
!
There are no conflicts of interest among all authors.
(+)-7′-Methoxylariciresinol (2): Sticky oil; [α]2D5 + 9.0 (c 0.07,
CHCl3); CD (c = 1.3 g/L, MeOH) Δ ε (nm) 228 (+ 73.3), 258 (− 4.0),
Sun Y-J et al. Four New Cytotoxic… Planta Med 2012; 78: 480–484

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DOI http://dx.doi.org/10.1055/s-0031-1298201
Published online January 26, 2012
Planta Med 2012; 78: 480–484
© Georg Thieme Verlag KG Stuttgart · New York ·
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Correspondence
Prof. Dr. Hui-Ming Hua
Key Laboratory of Structure-Based Drug Design & Discovery
Ministry of Education
School of Traditional Chinese Materia Medica
Shenyang Pharmaceutical University
Box 49
Shenyang 110016
Peopleʼs Republic of China
Phone: + 862423986465
Fax: + 862423986465
huimhua@163.com
Prof. Dr. Hong Chen
Tianjin Key Laboratory for Biomarkers of Occupational and
Environmental Hazard
Pharmacognosy Division
Medical College of Chinese Peopleʼs Armed Police Force
No. 222, Chenglin Road
Tianjin 300162
Peopleʼs Republic of China
Phone: + 862260578193
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