全 文 ： 2010 年 1 月 第 8 卷 第 1 期 Chin J Nat Med Jan. 2010 Vol. 8 No. 1 1

Chinese Journal of Natural Medicines 2010, 8(1): 0001−0005
doi: 10.3724/SP.J.1009.2010.00001
Chinese
Journal of
Natural
Medicines







·Original papers·
Propinic Lactones A and B, Two New Triterpenoids from
Schisandra propinqua var. propinqua and the Significance in
Biosythesis Pathway
LEI Chun, PU Jian-Xin, XIAO Wei-Lie, YANG Li-Bin, LIU Jing-Ping,
CHEN Ji-Jun, SUN Han-Dong *
State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese Academy of Sciences,
Kunming 650204, China
Available online 20 Jan 2010
[ABSTRACT] AIM: To study the chemical constituents of the aerial parts of Schisandra propinqua var. propinqua. METHOD: Silica
gel, C18 reversed phase silica gel and HPLC were used. The structures were elucidated by extensive spectroscopic methods. RESULT:
Two new triterpenoids, propinic lactone A (1) with 3, 4-seco-cycloartane skeleton, and propinic lactone B (2) possessing 3, 4:9,
10-seco-cycloartane skeleton, together with a known typical cycloartane triterpenoid, schizandronic acid (3), have been isolated and
identified. CONCLUSION: These two new triterpenoids serve as two important bridge intermediates from cycloartane triterpenoids to
Schisandra nortriterpenoids biogenetically.
[KEY WORDS] Schisandraceae; Schisandra; Schisandra propinqua var. propinqua; Triterpenoids
[CLC Number] R284.1 [Document code] A [Article ID] 1672-3651(2010)01-0001-05

1 Introduction
Schisandra nortriterpenoids are a group of structurally
intriguing triterpenoids with promising bioactivities produced
by the medicinally important genus schisandra in Schi-
sandraceae family. They mainly consist of schiartane[1],
18(13→14)-abeo-schiartane[2], 18-nor-schiartane[3], pre-
schisanartane[4], schisanartane[5], and wuweiziartane skele-
tons[6]. Compounds with these skeletons were theoretically
considered to be biogenetically related and all derived from
cycloartane backbone precursors[2, 4, 7]. However, there was
no obvious evidence to prove this biological pathway due to
the lack of convincible intermediates discovered to co-exist
with cycloartane and those nortriterpenoids[8]. From our re-
cent investigations, a new 3, 4-seco-cycloartane triterpenoid,
propinic lactone A (1), and a new 3, 4:9, 10-seco-cycloartane

[Received on] 02-May-2009
[Research Funding] This project was supported by the National
Natural Science Foundation (No. 30830115 and 20802082), the
Major State Basic Research Development Program of China (No.
2009CB522300 and 2009CB940900).
[*Corresponding author] SUN Han-Dong: Prof., Tel: 86-871-
5223251, Fax: 86-871-5216343, E-mail: hdsun@mail.kib.ac.cn
triterpenoid, propinic lactone B (2), were isolated together
with a known cycloartane triterpenoid, schizandronic acid
(3)[9] and many Schisandra nortriterpenoids from the stems of
Schisandra propinqua var. propinqua[9-12]. The discovery of
these two new triterpenoids could fill the biosynthesis gaps
from cycloartane to schiartane (3, 4:9, 10-seco-28
-norcycloartane) skeleton through 3,4-seco-and 3, 4:9, 10-
seco-cycloartane triterpenoid as key intermediates in the ge-
nus Schisandra. Herein, we report the identification of the
new compounds, and discuss the putative biosynthetic path-
ways from cycloartane to schiartane skeleton.
2 Materials and Methods
2.1 General
Petroleum ether (PE, 60-90°C), EtOAc, CHCl3, acetone,
methanol, and i-prOH were analytical grade and produced by
Sinopharm Chemical Reagent Co. Ltd., China. Silica gel
(200-300 mesh and 10-40 μm; Qingdao Marine Chemical,
Inc., China) and sephadex (General Electric Company, USA)
for column separation. Fractions were monitored by thin
layer chromatography (TLC), and spots were visualized by
spraying with 8% H2SO4 in EtOH, followed by heating. Op-
tical rotations: Horiba SEPA-300 spectropolarimeter. IR
spectra: BioRad FTS-135 spectrophotometer, KBr discs; in
LEI Chun, et al. /Chinese Journal of Natural Medicines 2010, 8(1): 1−5
2 Chin J Nat Med Jan. 2010 Vol. 8 No. 1 2010 年 1 月 第 8 卷 第 1 期

cm-1. 1D- and 2D-NMR Spectra: DRX-500 instruments; J in
Hz. HR-ESI-MS: VG AutoSpec-3000 spectrometers; in m/z.
2.2 Plant Material
Stems of S. propinqua var. propinqua were collected in
Tengchong Country, Yunnan Province, China, in July 2006,
and were identified by Prof. LI Xi-Wen, Kunming Institue of
Botany, Chinese Academy of Sciences. A voucher specimen
(No.20050823) was deposited at the State Key Laboratory of
Phytochemistry and Plant Resources in West China, Kun-
ming Institute of Botany, Chinese Academy of Sciences,
China.
2.3 Extraction and Isolation
The air-dried stems of S. propinqua var. propinqua (8 kg)
were extracted with 70% aqueous acetone (4 × 15 L, 3d each)
at room temperature. The solvent was removed in vacuo to
afford a crude extract (560 g), which was dissolved in H2O,
and then extracted successively with petroleum ether and
EtOAc. The EtOAc-soluble part (250 g) was purified by CC
(on SiO2 with CHCl3/acetone 1 → 0) to obtain six main frac-
tions (Fr. A–F). Fr.B was placed in acetone to crystallize
compound 3 (5 g). Fr.C (CHCl3/acetone 9: 1-8: 2, 29 g) was
purified by repeated CC, first on Sephadex LH-20 eluted with
MeOH, then on silica gel eluted by PE/i-prOH in gradient
system and followed by recrystallization in acetone to afford
1 (30 mg). Fr.D (CHCl3/acetone 8: 2-2: 1, 45 g) was purified
first by CC on silica gel with CHCl3/acetone 4:1 to obtain
small fractions of D1, D2 and D3. D2 was then subjected to
RP-18 in 30%-60% aqueous MeOH gradient system after
purified on Sephadex LH-20 eluted with MeOH to afford five
mixtures (D2-1-D2-5). D2-3 (40% aqueous MeOH) was pu-
rified on silica gel with PE/i-PrOH 5: 1 and followed by
semi-prep. HPLC (40% aqueous MeOH) to yield 2 (3 mg).
Propinic lactone A (1). Colorless needles. mp 172–
173°C. [α] 22.9 D + 86.73 (c 2.13, CH3OH/CHCl3 2:1); CD
(MeOH) λmax nm (Δε): 260.0 (+6.00), 247.5 (+5.20). IR (KBr)
νmax: 3 550, 2 970, 2 953, 1 736, 1 715, 1 446, 1 380, 1 359,
1 194, 1 130 cm–1. 1H and 13C NMR data, see Table 1,
OCH3: 3.60 (s), 51.3 (q); HR-ESI-MS (neg.): 499.3413
([M-H]–, C31H47O5–, calc. 499.342 3).
Propinic lactone B (2). Colorless solid. [α]19.8 D + 28.90
(c 0.15, MeOH); CD (MeOH) λmax nm (Δε): 220.0 (– 10.2).
IR (KBr) νmax: 3468, 2927, 1757, 1684, 1456, 1385, 1260,
1205, 1103, 1063, 1034, 914, 801 cm–1; 1H and 13C NMR
data, see Table 1. HR-ESI-MS (neg.): 531.296 6 ([M-H]–,
C30H43O8–, calcd. 531.295 7).
3 Results and Discussion
3.1 Structure elucidation
Compounds 1–3 (Fig.1) were isolated from 70% aqueous
acetone extract of the stems of S. propinqua var. propinqua.
Compound 3 was identified to be schizandronic acid, a typi-
cal cycloartane triterpenoid in genus schisandra, by compar-
ing its 13C NMR and DEPT spectra with the literature[9].
Compounds 1 and 2 are new triterpenoids related to cycloar-
tane as determined by comprehensive spectroscopic means
including 1D and 2D NMR.
Propinic lactone A (1) was obtained as colorless needles.
Its formula was established as C31H48O5 from HR-ESI-MS
(m/z 499.341 3 ([M-H]–, calcd. 499.342 3)) and 13C NMR
spectroscopic data (Table 1), requiring eight degrees of un-
saturation. The 1H NMR spectrum of 1 (Table 1) exhibited
signals of one typical AB coupled system at δH 0.58 (ABd, J
= 5.5 Hz, H-19α), 0.79 (ABd, J = 5.5 Hz, H-19β), and seven
methyl signals including one oxygenated singlet at δH 3.60 (s,
H3-OCH3), five aliphatic singlets at δH 1.94, 1.42, 1.40, 0.95,
0.92 and a doublet at δH 0.97 (d, J = 8.5 Hz, H3-21). The 13C
NMR (Table 1) and DEPT spectra showed the presence of
two ester carbons (δC 174.8,s; 166.3, s), one trisubstituent
double bond (δC 140.2, d) and 128.1(s), and seven methyl
groups including an oxygenated one at δC 51.3. All these
signals, plus eight degrees of unsaturation, suggested that
compound 1 was a methylated triterpenoid with five rings
including a three-member ring, as that of 3 possessing cyc-
loartane skeleton.
However, the 13C NMR data of 1 differed greatly from
those of compound 3. Three spin systems, H-24/H2-23/
H-22/H-20/H-17,21/H2-16/H2-15, H2-12/H2-11, and H-8/H2-
7/H2-6/H-5 in 1H,1H-COSY spectrum of 1 (Fig. 2 ), together
with five groups of HMBC correlations (Fig. 2 ) from H3-27
to C-24, C-25 and C-26, from H-22 to C-17, C-20, C-21,
C-23, C-24 and C-26, from H3-18 to C-12, C-13 and C-17,
from H3-28 to C-8, C-13, C-14 and C-15, and from H2-19 to
C-5, C-8, C-9, C-10 and C-11 building up the five rings of 1
as shown. This partial structure was almost the same as that
of kadsudilactone[13] with A ring cracked and a six-member
α-methyl-α, β-unsaturated-δ-lactone ring in the side chain
which was remarkably distinct from that of 3. In the HMBC
experiment (Fig. 2), correlations from H2-19 to C-1, from
both H2-1, H2-2 and H3-OCH3 to C-3, and from H-5 to C-4,
C-29 and C-30 indicated that the bond of C-3/C-4 in 1 broke
down followed by a methyl esterification at C-3. Thus, the
planar structure of compound 1 was established as a 3, 4-seco
cycloartane derivative.
The relative stereochemistry of compound 1 was deter-
mined to be the same as that of 3 and kadsudilactone on the
biosynthetic consideration, which was proved by ROESY
experiment. C-22 of 1 was assigned to be R configuration as
the CD spectrum showed a positive Cotton effect near 260
nm (Δε + 6.0), similar to that of kadsulactone.
Propinic lactone B (2) was analyzed to be C30H44O8 from
HR-ESI-MS (m/z 531.296 6 [M-H] –, calcd. 531.295 7) and it
required nine degrees of unsaturation. The 1H NMR spectrum
(Table 1) of 2 displayed five tertiary methyls (δH 1.80, 1.62,
and 1.24, 1.08, 0.99), a secondary methyl (δH 1.36, d, J = 6.0
Hz) and a characteristic ABX spin system ( δ 4.27 (d, J = 4.5
Hz, H(1)), 2.74 (d, J = 18.0 Hz, Hα(2)), and 2.99 (dd, J = 4.5,
18.0 Hz, Hβ(2)). The 13C NMR spectrum (Table 1) showed
signals for 30 carbons including six methyl groups, seven
LEI Chun, et al. /Chinese Journal of Natural Medicines 2010, 8(1): 1−5
2010 年 1 月 第 8 卷 第 1 期 Chin J Nat Med Jan. 2010 Vol. 8 No. 1 3

Table 1 1H and 13C NMR data of 1 and 2 (recorded with a Bruker DRX-500 MHz in C5D5N; J in Hz.)
Position 1 2
δ H (mult, J in Hz) δ C (mult) δ H (mult, J in Hz) δ C (mult)
1 1.60–1.64 (m, Ha) 31.1 (t) 4.27 (d, J = 4.5, Hβ) 81.9 (d)
3.20–3.28 (m, Hb)
2 3.07 – 3.11 (m, Ha) 32.6 (t) 2.74 (d, J =18.0, Hα) 36.6 (t)
2.43 – 2.47 (m, Hb) 2.99 (dd, J = 4.5, 18.0, Hβ)
3 174.8 (s) 175.3 (s)
4 75.1 (s) 84.9 (s)
5 2.10 (dd, J = 7.5, 17.5, Hα) 45.9 (d) 2.55 (dd, J = 4.0, 13.5, Hα ) 60.0 (d)
6 1.72 – 1.79 (overlapped, Hα) 25.5 (t) 1.26 – 1.32 (m, Hα ) 28.8 (t)
0.72 – 0.76 (m, Hβ) 1.59 – 1.65 (overlapped, Hβ )
7 1.00 – 1.04 (m, Hα) 26.2 (t) 2.80 – 2.85 (overlapped, Hα) 24.7 (t)
1.23 – 1.41 (overlapped, Hβ) 2.02 – 2.12 (overlapped, Hβ)
8 1.30 – 1.36 (overlapped, Hβ) 48.8 (d) 1.82 – 1.87 (overlapped, Hβ) 54.0 (d)
9 22.6 (s) 73.8 (s)
10 27.3 (s) 100.3 (s)
11 2.17 – 2.26 (overlapped, Hα) 26.7 (t) 1.79 – 1.86 (overlapped, Hα) 39.5 (t)
1.20 – 1.28 (overlapped, Hβ) 1.69 – 1.72 (overlapped, Hβ)
12 1.51 – 1.59 (overlapped, 2H) 33.2 (t) 2.28 – 2.34 (overlapped, Hα) 30.8 (t)
1.55 – 1.61 (overlapped, Hβ)
13 45.6 (s) 47.3 (s)
14 48.8 (s) 51.0 (s)
15 1.27 – 1.35 (overlapped, 2H) 36.3 (t) 4.30 – 4.36 (m, Hβ ) 77.1 (d)
16 1.68 – 1.75 (overlapped, Hα ) 27.1 (t) 2.28 – 2.34 (overlapped, Hα ) 40.4 (t)
1.29 – 1.34 (overlapped, Hβ ) 2.14 – 2.24 (overlapped, Hβ )
17 1.51 – 1.58 (overlapped, Hα ) 48.4 (d) 2.17 – 2.26 (overlapped, Hα ) 46.0 (d)
18 0.95 (s) 18.5 (q) 0.99 (s) 15.7 (q)
19 0.58 (ABd, J = 5.5, Hα) 31.5 (t) 1.98 – 2.07 (overlapped, 2H ) 48.1 (t)
0.79 (ABd, J = 5.5, Hβ )
20 1.95 – 2.01 (m) 39.5 (d) 2.14 – 2.24 (overlapped) 42.3 (d)
21 0.97 (d, J = 8.5) 13.1 (q) 1.36 (d, J = 6.0) 15.6 (q)
22 4.45 (ddd, J = 4.0, 4.5, 16.5) 80.5 (d) 4.10 (br. s) 73.9 (d)
23 2.20 – 2.27 (overlapped, Ha) 23.6 (t) 5.27 (br. s) 82.6 (d)
2.00 – 2.08 (m, Hb)
24 6.53 (d, J = 8.0) 140.2 (d) 7.19 (br. s) 148.7 (d)
25 128.1 (s) 130.2 (s)
26 166.3 (s) 174.9 (s)
27 1.94 (s) 17.3 (q) 1.80 (s) 10.7 (q)
28 0.92 (s) 19.8 (q) 1.62 (s) 13.1 (q)
29 1.42 (s) 32.0 (q) 1.08 (s) 23.0 (q)
30 1.40 (s) 26.7 (q) 1.24 (s) 29.5 (q)
OCH3 3.60 (s) 51.3 (q)



Fig. 1 Structures of 1–3
LEI Chun, et al. /Chinese Journal of Natural Medicines 2010, 8(1): 1−5
4 Chin J Nat Med Jan. 2010 Vol. 8 No. 1 2010 年 1 月 第 8 卷 第 1 期


Fig. 2 1H-1H COSY and selected HMBC correlations of 1 and 2

methylene carbons, eight methine carbons, two ester groups,
a tri-attributed double bond, three oxygenated tertiary car-
bons and two aliphatic tertiary carbons. Comparing these
signals with those of micrandilactone B[1,10] with the schiar-
tane carbon skeleton, it was found that signals of rings A-C,
the side chain, as well as that of ring F in 2 were almost the
same in the case of micrandilactone B, which was further
confirmed by the key 1H,1H-COSY and HMBC data as
shown in Fig. 2.
Detailed comparisons of 1D-NMR (Table 1) indicated
the main difference restricted in rings D and E. As an oxy-
genated tertiary carbon in micrandilactone B replaced by an
aliphatic one in 2 and one more methyl group appearing in 2,
there could be a methyl attributed at C-14 or C-15. Two key
HMBC correlations (Fig. 2) from H3-18 to C-12, C-13 and
C-17 and from H3-28 to C-8, C-13, C-14 and C-15 proved
that the methyl was attributed at C-14. Thus, compound 2
was actually a 3, 4: 9, 10-seco-cycloartane triterpenoid.
The configuration of CH3-18 was biogenetically β direc-
tion while H-17 was α direction. Thus CH3-28 was α oriented,
which was established by the key ROESY correlation of
H3-28/H-7α /H-16α /H-17α (Fig. 3). The H-15 was assigned
to be β orientation by the cross-peak of H3-18/H-8/H-11β/H-
15β in the ROESY experiment (Fig. 3). And the other con-
figuration was the same as that of micrandilactone B, which
was deduced by the similar proton coupling constants and
ROESY correlation data, as well as CD experiment.
3.2 Putative biogenetic pathway from cycloartane to
schiartane skeleton
As the oxidation degree deepening, cycloartane back-
bone was presumed to be oxygenated into schiartane skeleton


Fig. 3 Selected ROESY correlations of 2

Scheme 1 Proposed biosynthetic pathway from 3 to micrandilactone B
LEI Chun, et al. /Chinese Journal of Natural Medicines 2010, 8(1): 1−5
2010 年 1 月 第 8 卷 第 1 期 Chin J Nat Med Jan. 2010 Vol. 8 No. 1 5

through ring A opened at bond of C-3/C-4, three-member ring
cleavage occurred at C-9/C-10, and then oxidative de-
carboxylation occurred of CH3-28. Compounds 3, 1, 2, and
micrandilactone B were representive compound possessing
cycloartane, 3,4-seco-cycloartane, 3, 4:9, 10-seco-cycloartane
and schiartane (3, 4:9, 10-seco-28-norcycloartane) skeleton,
respectively. Their co-existence in S. propinqua var. propin-
qua brought obvious evidence to fill in the gap between the
putative biosynthetic sequences from cycloartane to schiar-
tane skeleton (Fig. 3). First, compound 3 may be hydroxyl-
ized at C-22 followed by dehydration, producing the
six-member α-methyl-α, β-unsaturated-δ-lactone ring in the
side chain to produce kadsulactone[13]. Then, ring A of kad-
sulactone disconnected at the bonds of C-3/C-4 followed by
methyl esterified at COOH-3 and hydroxylized at C-4 to
produce compound 1. After a few hydroxylation modifica-
tions happened on 1 (intermediate A), the three-member ring
was broken at C-9/C-10 to build the seven-member ring C
(intermediate B). Ester-exchange reaction formed two
five-member lactone rings A and F, and a Michael addition
reaction (intermediate C) was finished to form the furan ring
B; compound 2 was thus obtained. Micrandilactone B was
finally produced through an oxidative decarboxylation of
CH3-28 (intermediate D). It’s the first time to discover com-
pounds with 3, 4-seco-cycloartane and 3, 4: 9,
10-seco-cycloartane skeletons co-existing with cycloartane
and schiartane backbones in the same source.
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合蕊五味子中两个新的三萜内酯及其在生物合成途径中的意义
雷 春, 普建新, 肖伟烈, 杨黎彬, 刘靖平, 陈纪军, 孙汉董*
中国科学院昆明植物研究所植物化学与西部植物资源持续利用国家重点实验室, 昆明 650204
【摘 要】 目的：研究合蕊五味子 (Schisandra propinqua var. propinqua) 地上部分化学成分。方法：利用正反相硅胶、高
效液相色谱等现代分离技术进行分离, 利用 IR, UV, MS 和 NMR 等现代波谱技术手段鉴定了它们的结构。结果：分离得到两个
分别具有 3,4-seco-cycloartane 和 3, 4:9, 10-seco-cycloartane 型骨架的新三萜内酯：propinic lactones A (1) 和 B (2); 同时分离得到
了一个典型的 cycloartane 骨架三萜类化合物。结论：这两个新化合物在生源合成途径上具有重要意义, 它们可能是连接
cycloartane 骨架三萜和 schisandra 降三萜骨架的重要中间体。
【关键词】 五味子科; 五味子属; 合蕊五味子; 三萜类化合物

【基金项目】 国家自然科学基金 (No. 30830115, 20802082), 国家重大基础研究发展项目基金 (No. 2009CB522300,
2009CB940900)