全 文 ： 374 Chin J Nat Med Sep. 2012 Vol. 10 No. 5 2012 年 9 月 第 10 卷 第 5 期

Chinese Journal of Natural Medicines 2012, 10(5): 0374−0377
doi: 10.3724/SP.J.1009.2012.00374
Chinese
Journal of
Natural
Medicines







A new cadinane sesquiterpene from the rhizomes
of Alpinia officinarum
XU Sheng-Mei1, 2, HUANG Xiao-Jun1, 2, WANG Ying1, 2*, YE Wen-Cai1, 2, 3*
1Institute of Traditional Chinese Medicine & Natural Products, Jinan University, Guangzhou 510632, China;
2Guangdong Province Key Laboratory of Pharmacodynamic Constituents of TCM and New Drugs Research, Jinan University, Guang-
zhou 510632, China;
3Department of Phytochemistry, China Pharmaceutical University, Nanjing 210009, China
Available online Sep. 2012
[ABSTRACT] AIM: To investigate the chemical constituents of the rhizomes of Alpinia officinarum. METHODS: Compounds were
isolated by various column chromatographic methods, and their structures were identified based on their physicochemical properties
and spectral data. RESULTS: A cadinane sesquiterpene, alpiniaterpene A (1), was isolated. Its structure with absolute configuration
was established by means of HR-ESI, NMR, and quantum chemical CD calculation. CONCLUSION: Compound 1 is a new com-
pound.
[KEY WORDS] Alpinia officinarum; Zingiberaceae; Sesquiterpene; Alpiniaterpene A; Absolute configuration
[CLC Number] R284.1 [Document code] A [Article ID] 1672-3651(2012)05-0374-04

1 Introduction
The plant Alpinia officinarum Hance (Zingiberaceae) is
widely cultivated in southern China. The rhizomes of A. offi-
cinarum are used as a traditional Chinese medicine for their
anti-inflammatory [1], antioxidant [2], anti-proliferative [3],
anticancer [4], and antiemetic [5] effects. Previous phyto-
chemical studies on this herb resulted in the isolation of
monoterpenes, diarylheptanoids, flavonoids and phenylpro-
panoids [6-8]. In order to assess the chemical and biological
diversity of the medicinal plants in the southern China, the
phytochemical investigation on the rhizomes of A. officina-
rum was conducted. As a result, a new cadinane sesquiter-
pene, alpiniaterpene A (1) (Fig. 1), was isolated. Its structure
with absolute configuration, was established by means of

[Received on] 27-Mar.-2011
[Research funding] This project was supported financially by the
Program for Changjiang Scholars and Innovative Research Team in
the University (No. IRT0965), the Team Project of Natural Science
Foundation of Guangdong Province (No. 8351063201000003), and
the Science and Technology Development Fund of Macau Special
Administrative Region (No. 013/2008/A1).
[*Corresponding author] YE Wen-Cai: Prof., Tel: 86-20-85221559,
E-mail: chywc@yahoo.com.cn; WANG Ying: Associate Prof., Tel:
86-20-85221559, E-mail: wangying_cpu@163.com
These authors have no any conflict of interest to declare.
HR-ESI-MS, NMR, and quantum chemical CD calculation.
Herein, the isolation and structural elucidation of the new
compound are described.

Fig. 1 Chemical structure and key 2D NMR correlations of
compound 1
2 Results and Discussion
Compound 1 was obtained as an amorphous powder. The
molecular formula of 1 was determined to be C16H22O4 by its
HR-ESI-MS at m/z 277.144 3 [M − H]− (Calcd. 277.144 5).
The UV spectrum of 1 showed the absorption maximum at
224 nm. The IR spectrum indicated the presence of hydroxyl
(3 442 cm−1) and carbonyl (1 713 cm−1) groups. The NMR
spectra of 1 indicated the presence of signals due to two car-
bonyl groups (δC 183.3 and 169.8), a trisubstituted double
bond [δH 6.91 (1H, s); δC 144.2 and 130.9], an exocyclic dou-
ble bond [δH 4.71 (1H, br s) and 4.61 (1H, br s); δC 153.5 and
105.0], a methoxyl [δH 3.69 (3H, s); δC 52.2], and a methyl
[δH 1.16 (3H, d, J = 6.8 Hz); δC 18.0]. With the aid of 1H-1H
XU Sheng-Mei, et al. /Chinese Journal of Natural Medicines 2012, 10(5): 374−377
2012 年 9 月 第 10 卷 第 5 期 Chin J Nat Med Sep. 2012 Vol. 10 No. 5 375

COSY, HSQC, and HMBC experiments, all of the 1H and 13C
NMR signals of 1 were assigned as shown in Table 1.
Table 1 1H and 13C NMR spectral data of 1 in CD3ODa, b
Position 1H 13C
1 2.31 38.5
2 α 1.39
β 2.05
26.5
3 α 2.21
β 2.43 dd (15.5, 4.5)
25.4
4 - 130.9
5 6.91 s 144.2
6 2.25 49.7
7 2.29 41.6
8 α 1.51
β 2.08 d (2.8)
31.3
9 2.18 dd (11.0, 4.5) 32.9
10 - 153.5
11 - 169.8
12 2.65 dq (10.5, 6.9) 40.2
13 - 183.3
14 1.16 d (6.8) 18.0
15 a 4.61 br s 105.0
b 4.71 br s
16 3.69 s 52.2
a Assignments were established by interpretation of the 1H-1H COSY,
HSQC, and HMBC spectra.
b Overlapped signals are reported without designating multiplicity.

The 1H and 13C NMR signals of 1 were similar to those
of (−)-cadin-4, 10(15)-dien-11-oic acid [9], indicating that 1
possessed the same cadinane sesquiterpenoid skeleton. The
HMBC correlations between H-3 and C-5/C-11, between H-5
and C-1/C-3/C-7/C-11, between H-14 and C-7, as well as
between H-15 and C-1/C-9 (Fig. 1) further supported the
above assignment. Different from (−)-cadin-4, 10(15)-dien-
11-oic acid, the 1H and 13C NMR data of 1 showed the pres-
ence of a methyl ester [δH 3.69 (3H, s); δC 169.8 and 52.2]
instead of the carboxyl group at C-11, as well as the presence
of a carboxyl carbon (δC 183.3) instead of the C-13 methyl
group. The above results were further confirmed by the
HMBC correlations between H3-16 and C-11, and between
H-14 and C-13. Therefore, the planar structure of 1 was con-
structed as shown in Fig. 1.
In the 1H NMR spectrum of 1, the signal assigned to H-5
appeared as a singlet [δH 6.91 (1H, s)], which indicated that
the two six-membered rings in 1 were fused in a trans form
reference [10]. Unfortunately, the splitting patterns of H-1, H-3,
H-6, and H-7 could not be recognized due to the overlapping
signals in the region δH 2.21-2.31. In order to establish the
stereostructure of 1, a quantum chemical ECD calculation
method was conducted by Gaussian 09 software. The eight
potential stereo-isomers of 1 are shown in Fig. 2. Prelimi-
nary conformational distribution search of each possible con-
figuration was performed by Syby18.0 software using the
Tripos force field. The corresponding minimum geometries
were further fully optimized by using DFT at B3LYP/6-
31G(d) level as implemented in the Gaussian 09 program
package. The stable conformers obtained were submitted to
ECD calculation by the TDDFT [B3LYP/6-31++G(2d, 3p)]
method. The overall predicted ECD spectra of the eight pos-
sible isomers were subsequently compared with the experi-
mental one, respectively. As a result, the 1S, 6S, 7R, and 12R
isomer revealed a good agreement between the calculated and
the measured ECD curves (Fig. 2). Thus, the absolute con-
figuration of 1 was unambiguously established as 1S, 6S, 7R,
and 12R.
3 Experimental
3.1 Equipment and chemicals
Melting point was obtained on an X-5 micromelting
point detector (uncorrected). Optical rotation value was
measured on a JASCO P-1020 digital polarimeter at room
temperature. UV spectrum was recorded on a JASCO V-550
UV/VIS spectrophotometer. IR spectrum (KBr) was meas-
ured on a JASCO FT/IR-480 plus Fourier transform infrared
spectrometer. 1D and 2D NMR (1H NMR, 13C NMR, 1H-1H
COSY, DEPT, HSQC, HMBC and NOESY) spectra were
recorded on Bruker AV-400 spectrometer (Bruker, Germany).
CD spectrum was recorded on a JASCO J-810 spectropo-
larimeter. All calculations were performed by the Gaussian
09 program package. HR-ESI-MS data were obtained using
an Agilent 6210 accurate-mass time-of-flight LC/MS spec-
trometer. Column chromatographic (CC) separations were
performed using silica gel (200−300 mesh, Qingdao Haiyang
Chemical Group Corporation, Qingdao, China) and Sephadex
LH-20 (Pharmacia Biotech AB, Uppsala, Sweden).
3.2 Plant material
The rhizomes of Alpinia officinarum Hance were col-
lected in Xuwen County, Guangdong Province, China, in
October 2010, and authenticated by Prof. ZHOU Guang-
Xiong (Institute of Traditional Chinese Medicine & Natural
Products, Jinan University). A voucher specimen (No.
101029) was deposited in the Institute of Traditional Chinese
Medicine & Natural Products, Jinan University, Guangzhou,
China.
3.3 Extraction and isolation
The air-dried rhizomes of Alpinia officinarum (20 kg)
were powdered and extracted with 95% (V/V) EtOH at room
temperature. The solution was evaporated under vacuum to
yield a residue (3.7 kg). The crude EtOH extract was sus-
pended in water and partitioned successively with petroleum
ether (b.p. 60−90 ºC), chloroform, and n-BuOH, respectively.
The chloroform extract (530 g) was subjected to silica
gel CC using gradient mixtures of petroleum ether-EtOAc
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376 Chin J Nat Med Sep. 2012 Vol. 10 No. 5 2012 年 9 月 第 10 卷 第 5 期


Fig. 2 Eight possible isomers of 1 and their calculated CD spectra as well as the experimental CD spectrum of 1
(100 : 0 to 0 : 100) as eluent to yield twenty-one fractions (Fr.
1−21). Fr. 15 (34 g) was further separated by silica gel col-
umn using petroleum ether−EtOAc (100 : 0 to 1 : 1) as eluent
and purified on Sephadex LH-20 column (MeOH) to afford
compound 1 (15 mg).
Alpiniaterpene A (1) Amorphous powder; mp > 300 ºC;
C16H22O4; [α]25 D −124.09° (c 0.87, MeOH); UV (MeOH) λmax:
224 nm; IR (KBr) νmax: 3 442, 2 930, 1 713, 1 651, 1 439,
1 290, 1 210, 889, 748 cm−1; HR-ESI-MS m/z 277.144 3 ([M
− H]−, C16H21O4; Calcd. 277.144 5); 1H and 13C NMR data
see Table 1.
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XU Sheng-Mei, et al. /Chinese Journal of Natural Medicines 2012, 10(5): 374−377
2012 年 9 月 第 10 卷 第 5 期 Chin J Nat Med Sep. 2012 Vol. 10 No. 5 377

高良姜根茎中一个新的杜松烷型倍半萜
徐胜梅 1, 2, 黄晓君 1, 2, 王 英 1, 2*, 叶文才 1, 2, 3*
1暨南大学中药与天然药物研究所, 广州 510632;
2中药药效物质基础及创新药物研究广东省高校重点实验室, 广州 510632;
3中国药科大学天然药物化学教研室, 南京 210009
【摘 要】 目的：对高良姜(Alpinia officinarum Hance)根茎的化学成分进行研究。方法：运用多种色谱技术分离纯化, 通过
理化常数和光谱数据鉴定化合物的结构。结果：分离鉴定了 1 个杜松烷型倍半萜类化合物, 命名为 alpiniaterpene A, 此外还利用
量子化学计算方法对该化合物的绝对构型进行了确证。结论：化合物 1 为新化合物。
【关键词】 高良姜; 姜科; 倍半萜; Alpiniaterpene A; 绝对构型

【基金项目】 教育部长江学者创新团队项目(No. IRT0965)；广东省自然科学基金团队项目(No. 8351063201000003)；澳门特别
行政区科学技术发展基金(No. 013/2008/A1)