全 文 ： 2010 年 5 月 第 8 卷 第 3 期 Chin J Nat Med May 2010 Vol. 8 No. 3 177

Chinese Journal of Natural Medicines 2010, 8(3): 0177−0179
doi: 10.3724/SP.J.1009.2010.00177
Chinese
Journal of
Natural
Medicines







A New Cadinane Sesquiterpenoid Lactone from
Lepidozia reptans
ZHANG Yan-Li, GUO Dong-Xiao, WANG Lei, LOU Hong-Xiang*
Department of Natural Products Chemistry, School of Pharmaceutical Sciences, Shandong University, Jinan 250012, China
Available online May 2010
[ABSTRACT] AIM: To study the chemical constituents of Lepidozia reptans (L.) Dumont. METHODS: The chemical constituents
were isolated and purified with column chromatography and their structures were elucidated on the basis of 1D and 2D NMR analysis.
RESULTS: Three compounds were obtained and identified as 5α-hydroxy-9α,10α-epoxycadinan-3-en-2β,14-olide (1), abieslactone
(2), and 24, 25-dihydroabieslactone (3). CONCLUSION: Compound 1 is a new cadinane sesquiterpenoid lactone, and compounds 2
and 3 have been isolated from this genus for the first time.
[KEY WORDS] Liverwort; Lepidozia reptans; Cadinane sesquiterpenoid lactone; Chemical constituents
[CLC Number] R284.1 [Document code] A [Article ID] 1672-3651(2010)03-0177-03

1 Introduction
Lepidozia reptans (L.) Dumont is a kind of liverwort be-
longing to the family of Lepidoziaceae which has been
proven to be a rich source of unique terpenoids and aromatic
compounds [1]. Several terpenoids from the essential oil and
ethyl ether extract of L. reptans have been reported[2]. In the
course of our phytochemical investigations on Chinese liv-
erworts[3], a new sesquiterpenoid lactone, 5α-hydroxy-9α,
10α-epoxycadinan-3-en-2β,14-olide (1), and two triterpene
lactones, abieslactone (2)[4-5] and 24, 25-dihydroabieslactone
(3)[4-5] were isolated from Lepidozia reptans.
2 Results and discussion
Compound 1 was obtained as a white powder. The
molecular formula C15H20O4 was deduced from its HR-ESI-MS
(m/z 265.142 6 [M + H]+, calcd. 265.143 4). IR absorption
bands at 3 485 and 1 750 cm-1 indicated the existence of a
hydroxyl and a five-membered lactone, respectively. The 1H
NMR spectrum (Table 1) disclosed the presence of an iso-
propyl group at δH 0.95 (3H, d, J = 6.0 Hz), 1.02 (3H, d, J =

[Received on] 18-Dec-2009
[Research Funding] This project was supported by the National
Natural Science Foundation of China (Nos. 30730109, 30925038)
[*Corresponding author] LOU Hong-Xiang: Prof., Tel:
86-531-88382012, Fax: 86-531-88382019, E-mail: lou-
hongxiang@sdu.edu.cn
6.0 Hz) and 1.93 (1H, m), a vinyl methyl at δH 1.89 (3H, d, J
= 1.8 Hz), an isolated olefinic proton at δH 5.67 (1H, t, J =
1.8 Hz), three oxymethine protons at δH 5.30 (1H, br d, J =
9.6 Hz), δH 4.10 (1H, t, J = 7.8 Hz), and δH 3.67 (1H, br s),
and a hydroxyl proton at δH 1.58 (1H, d, J = 7.8 Hz). The 13C
NMR (Table 1) resolved 15 carbon signals, which were clas-
sified by chemical shifts and HSQC spectrum as three me-
thyls (one vinyl methyl), one methylene, eight methines (an
olefinic one and three oxygenated ones), and three quaternary
carbons (one oxegenated, one carboyl, and one olefinic car-
bon). In the 1H-1H COSY spectrum, the observed correlations
of H-3/H-2, H-2/H-1, H-1/H-6, H-6/H-5, H-5/-OH, H-6/H-7,
H-7/H-11, H-11/H3-12, H-11/H3-13, H-7/H2-8, H2-8/H-9
were fully consistent with the partial structure (shown as
bolden lines in Fig. 2) of 1. In the HMBC spectrum (Fig. 2),
the proton of the hydroxyl group at C-5 correlated with C-4
(δC 144.1), allowing the connectivity of C-5 (δC 66.4) with
C-4. The methyl signal at δH 1.89 exhibited correlations with
C-3 (δC 120.4), C-4 and C-5, indicating that the methyl group
was attached to C-4. The HMBC correlations of H-1, H-6,
H2-8, and H-9 with the quaternary carbon C-10 (δC 56.5)
demonstrated the attachment of C-10 with C-1 and C-9,
which was further confirmed by the correlation of H-1 with
C-9. The HMBC correlations of H-2 and H-9 with C-14 (δC
173.1) indicated the connectivity of C-14 and C-10, as well
as the linkage of C-2 and C-14 via an oxygen atom to form a
five-membered lactone. The remaining unsaturation degree
ZHANG Yan-Li, et al. /Chinese Journal of Natural Medicines 2010, 8(3): 177−179
178 Chin J Nat Med May 2010 Vol. 8 No. 3 2010 年 5 月 第 8 卷 第 3 期



Fig. 1 Structures of compounds 1−3

and the chemical shifts of C-9 (δC 58.7) and C-10 (δC 56.5)
showed the presence of an epoxy linkage between C-9 and
C-10. On the basis of the above discussion, the cadinane
skeleton[6-7] and locations of the functional groups of the
compound were established for 1.
The relative configuration of 1 was elucidated by
NOESY experiments and the coupling constants. In the
NOESY spectrum, the observed correlations of H-7/H-1,
H-7/H-9 indicated them to be on the same side of the mole-
cule, and H-6 and the isopropyl group were located on the
same side based on the correlations of H-6/CH3-13. The large
coupling constant between H-2 and H-1 (J = 9.6 Hz) sug-
gested them to be on the opposite side. Similarly, H-5 and
H-6 were also on the opposite side of the molecule. Thus, the
structure of 1 was established to be 5α-hydroxy-9α,10α-
epoxycadinan-3-en-2β,14-olide. The other two compounds
were identified as abieslactone (2) and 24,
25-dihydroabieslactone (3) on the basis of comparison of
their 1H and 13C NMR spectroscopic data with those reported.
3 Experimental
3.1 General experimental procedures
Optical rotations were measured on a GYROMAT-HP
polarimeter. UV spectra were determined on a Shimadzu
UV-2450 spectrophotometer. CD spectra were acquired on a
Chirascan spectropolarimeter. IR spectra were recorded on a
Thermo-Nicolet 670 spectrophotometer using KBr disks.
NMR spectra were measured on a Bruker Avance DRX-600
spectrometer operating at 600 (1H) or 150 (13C) MHz with
TMS as internal standard. HR-ESI-MS was carried out on a
LTQ-Orbitrat XL mass spectrometer. All solvents used were
of analytical grade. Column chromatography was performed
on either silica gel (200−300 mesh; Qingdao Marine Chemi-
cal, Inc., Qingdao, China) or Sephadex LH-20 (25−100 μm;
Pharmacia). Semipreparative HPLC was performed on an
Agilent 1100 liquid chromatograph with a ZORBAX Eclipse
XDB-C18, 4.6 mm × 150 mm column. Fractions were moni-
tored by TLC, and spots were visualized under UV (254 nm)
light and by heating silica gel plates which were sprayed with
10% H2SO4 in EtOH.
3.2 Plant material
Lepidozia reptans was collected from Mount Jiaozi,
Yunnan Province, China and identified by Prof. ZHU
Rui-Liang (East China Normal University, Shanghai). A
voucher specimen (No. 20060627) has been deposited at the
Department of Natural Products Chemistry, School of Phar-
maceutical Sciences, Shandong University.
3.3 Extraction and isolation
Dried and powdered liverwort Lepidozia reptans (1.5 Kg)
was exhaustively extracted with 90% EtOH (5 L × 3). The
concentrated extract (45 g) was partitioned successively with
Et2O (150 mL × 3) and n-BuOH (150 mL × 3). The Et2O
extract (20 g) was subjected to silica gel column chromatog-
raphy (petroleum ether/ acetone gradient) to give five frac-
tions, A−E. Fraction B, eluted with petroleum ether/acetone
(20 : 1), was further purified with Sephadex LH-20
(CHCl3/MeOH) column chromatography and
semi-preparative HPLC (70% MeOH/H2O, 0.8 mL·min−1) to
afford compound 1 (2.5 mg). Fraction C, eluted with petro-
leum ether/acetone (30 : 1), was further purified with silica
gel column chromatography and semi-preparative HPLC
(100% MeOH, 0.8 mL min−1) to afford compounds 2 (2.8 mg)
and 3 (3.1 mg).



Fig. 2 Key 1H-1H COSY (▬) and HMBC (H→C) correla-
tions of 1

4 Identification
5α-hydroxy-9α,10α-epoxycadinan-3-en-2β,14-olide (1):
White amorphous powder; [α]D20 −36.25° (c 0.02, MeOH);
CD (MeOH) λmax (Δε): 228 (+2.3), 203 (+3.5) nm; UV
(MeOH) λmax (log ε): 203 (3.92) nm, IR (KBr) ν: 3 485, 2 959,
2 925, 2 859, 1 750, 1 261, 1 074 cm−1; C15H20O4;
HRESI-MS m/z: 265.142 6 [M + H]+ (calcd. for C15H21O4 m/z
265.143 4); 1H and 13C NMR see Table 1.
Abieslactone (2): Colorless crystal; C31H48O3; mp
238−242 °C; 1H NMR (600 MHz , CDCl3) δH: 0.93 (3H, s,
H3-28), 0.95 (3H, s, H3-30), 0.96 (3H, s, H3-29), 1.00 (3H, d,
J = 6 Hz, H3-21), 1.01 (3H, s, H3-19), 1.03 (3H, s, H3-18),
1.92 (3H, s, H3-27), 2.82 (1H, m, H-3), 3.31 (3H, s, OCH3),
4.99 (1H, m, H-23), 5.53 (1H, m, H-27), 7.00 (1H, m, H-24);
ZHANG Yan-Li, et al. /Chinese Journal of Natural Medicines 2010, 8(3): 177−179
2010 年 5 月 第 8 卷 第 3 期 Chin J Nat Med May 2010 Vol. 8 No. 3 179

Table 1 1H NMR (600 MHz) and 13C NMR (150 MHz) data
of compound 1 (J in Hz) in CDCl3
Position δC δH
1 36.4 2.91 (1H, dd, J = 9.6, 7.8)
2 74.5 5.30 (1H, br d, J = 9.6 )
3 120.4 5.67 (1H, t, J = 1.8 )
4 144.1
5 66.4 4.10 (1H, t, J = 7.8 )
6 36.9 2.23 (1H, dt, J = 7.8, 2.4)
7 40.4 1.23 (1H, m)
8 24.6 1.69 (1H, ddd, J = 15.6, 13.8, 1.8)
2.43 (1H, dd, J = 15.6, 4.2)
9 58.7 3.67 (1H, br s)
10 56.5
11 30.2 1.93 (1H, m)
12 21.7 0.95 (3H, d, J = 6.0)
13 22.1 1.02 (3H, d, J = 6.0)
14 173.1
15 19.5 1.89 (3H, d, J = 1.8)
5-OH 1.58 (1H, d, J = 7.8)

13C NMR (150 MHz, CDCl3) δC: 30.0 (C-1), 23.0 (C-2), 85.9
(C-3), 37.6 (C-4), 42.8 (C-5), 22.8 (C-6), 121.6 (C-7), 149.8
(C-8), 48.5 (C-9), 35.7 (C-10), 20.3 (C-11), 35.3 (C-12), 43.7
(C-13), 52.8 (C-14), 33.2 (C-15), 28.6 (C-16), 53.9 (C-17),
23.8 (C-18), 24.5 (C-19), 33.4 (C-20), 18.3 (C-21), 40.4
(C-22), 79.0 (C-23), 149.8 (C-24), 129.4 (C-25), 174.5
(C-26), 10.7 (C-27), 23.8 (C-28), 28.7 (C-29), 30.9 (C-30),
56.8 (OCH3); ESI-MS (int. rel) m/z: 483.4 [M + H]+, 505.4
[M + Na]+.
24, 25-dihydroabieslactone (3): Colorless crystal; C31H50O3;
mp 195−199 °C; 1H NMR (600 MHz , CDCl3) δH: 0.91 (3H,
s, H3-28), 0.93 (3H, s, H3-30), 0.95 (3H, s, H3-29), 0.95 (3H,
d, J = 6 Hz, H3-21), 1.01 (3H, s, H3-19), 1.04 (3H, s, H3-18),
1.28 (3H, d, J = 7.8 Hz, H3-27), 2.81 (1H, m, H-3), 3.31 (3H,
s, OCH3), 4.65 (1H, m, H-23), 5.52 (1H, m, H-7); 13C NMR
(150 MHz, CDCl3) δC: 30.2 (C-1), 23.2 (C-2), 86.0 (C-3),
37.8 (C-4), 43.0 (C-5), 23.0 (C-6), 121.7 (C-7), 148.7 (C-8),
48.7 (C-9), 35.8 (C-10), 20.5 (C-11), 35.5 (C-12), 43.9
(C-13), 53.0 (C-14), 33.4 (C-15), 28.8 (C-16), 54.1 (C-17),
24.0 (C-18), 24.7 (C-19), 33.6 (C-20), 18.5 (C-21), 42.7
(C-22), 76.2 (C-23), 36.6 (C-24), 33.6 (C-25), 180.4 (C-26),
16.1 (C-27), 24.0 (C-28), 28.9 (C-29), 31.0 (C-30), 57.0
(OCH3); ESI-MS (int. rel) m/z: 485.4 [M + H]+, 507.4 [M +
Na]+.
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指叶苔中的一个新倍半萜内酯化合物
张艳丽, 郭东晓, 王 蕾, 娄红祥*
山东大学药学院天然药物化学教研室, 济南 250012
【摘 要】 目的：对指叶苔的化学成分进行分离和鉴定。方法：运用柱色谱方法分离纯化化合物, 通过波谱数据和理化性
质对其进行结构鉴定。结果：分离获得了 3个化合物, 分别为：5α-hydroxy-9α,10α-epoxycadinan-3-en-2β,14-olide (1), abieslactone
(2), 和 24,25-dihydro-abieslactone (3)。结论：化合物 1 为新化合物, 化合物 2 和 3 为首次从该植物中分离得到。
【关键词】 苔藓; 指叶苔; 杜松烷型倍半萜内酯; 化学成分

【基金项目】 国家自然科学基金(Nos. 30730109, 30925038)