Compounds from the roots of Jasminum sambac

Article abstract of DOI:10.1080/10286020.2012.738675

Four new compounds (+)-jasminoids A (1), B (2), C (3), and D (4), together with seven known compounds, were isolated from the roots of Jasminum sambac. Their structures were identified using spectroscopic methods. This study provides a better understanding to the chemical composition of J. sambac roots that have been thought to be one ingredient of an ancient prescription Ma-Fei-San.

Full text of DOI:10.1080/10286020.2012.738675

Journal of Asian Natural Products Research
Vol. 14, No. 12, December 2012, 1180–1185
Compounds from the roots of Jasminum sambac
Lin-Hong Zengab1, Min Huc1, Yong-Ming Yana, Qing Lua and Yong-Xian Chenga*
aState Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of
Botany, Chinese Academy of Sciences, Kunming 650204, China; Graduate University of Chinese
b
Academy of Sciences, Beijing 100039, China; cResearch Center of Molecular Medicine of Kunming
University, Kunming 650214, China
(Received 28 June 2012; final version received 8 October 2012)
Four new compounds (þ)-jasminoids A (1), B (2), C (3), and D (4), together with seven
known compounds, were isolated from the roots of Jasminum sambac. Their structures
were identified using spectroscopic methods. This study provides a better
understanding to the chemical composition of J. sambac roots that have been thought
to be one ingredient of an ancient prescription ‘Ma-Fei-San’.
Keywords: Jasminum sambac; jasminoids A–D; sesquiterpenoids; iridoids
1. Introduction
composition of J. sambac roots. In this
paper, we report the isolation and struc-
tural elucidation of four new compounds.
Jasminum sambac (Oleaceae) is an ever-
green vine or shrub native to south and
southeast Asia. It has been widely
cultivated for its attractive and fragrant
flowers. In China, the flower is processed
and used for perfumes and the main
ingredient in jasmine tea [1]. The root is
a traditional Chinese medicine with
anesthetic and analgesic effects and used
for the treatment of insomnia, headache,
decayed tooth, and injuries from falls [2].
Interestingly, the root is thought to be one
important ingredient of Ma-Fei-San, i.e.
the powder for anesthesia, which is an
ancient prescription created by Tuo Hua
and used for surgeries due to its significant
anesthetic and analgesic effects, which
aroused our great interest. Previous studies
indicated the presence of lignans, terpe-
noids, and flavonoids [3,4]. The extract of
the roots has been proved to have sedative
effects in clinical trials [5]. However, the
further study needs to be explored to get a
better understanding of the chemical
2. Results and discussion
Compound 1 had the molecular formula
C15H20O2 derived from its HR-ESI-MS at
m/z 231.1384 [M–H]2, indicating six
degrees of unsaturation. The IR spectrum
showed the absorption bands for OH
groups (3425 cm21) and a phenyl ring
(1630 cm21). The 13C NMR and DEPT
spectra gave 15 carbon signals including
two methyl, five methylene (one oxyge-
nated methylene and one olefinic methyl-
ene), two methine, and six olefinic
quaternary carbons, indicating that 1 is a
sesquiterpenoid similar to cinalbicol [6].
The difference was that a methyl group in
cinalbicol was replaced by a hydroxy-
methyl, corresponding to the chemical
shift of C-13 (d 65.8). This was also
supported by the HMBC correlations of H-
8/C-11, and H-12/C-7, C-13. The deter-
mination of configuration at C-4 is
*Corresponding author. Email: yxcheng@mail.kib.ac.cn
ISSN 1028-6020 print/ISSN 1477-2213 online
q 2012 Taylor & Francis
http://dx.doi.org/10.1080/10286020.2012.738675
http://www.tandfonline.com

Journal of Asian Natural Products Research
1181
challengeable. There is only one chiral
carbon in compound 1, and the stereo-
chemistry at C-4 was tentatively assigned
as S-configuration by comparison of the
specific rotation of 1 with that of
cinalbicol. Thus, the structure of 1 was
deduced as shown in Figure 1, with a
trivial name (þ)-jasminoid A.
C-11, H3-14/C-6, and H-4/C-5, C-6
(Figure 1). ROESY correlation of H3-14/
H3-15 established the relative configur-
ation of 2 as shown in Figure 1. Therefore,
the structure of 2 was determined and
given a name jasminoid B.
Compound 3 was found to have the
molecular formula C17H30O8 from its HR-
ESI-MS at m/z 361.1866 [M–H]2. The
13C NMR and DEPT spectra displayed 17
carbons, 11 of which were attributed to
one methoxy group, one methyl, four
methylene including two oxygenated ones,
and five methine (one resonated at d
100.9), the other six carbons were
characteristic of a glucosyl moiety.
1H–1H COSY correlations of H-4/H-11,
H-4/H-5/H-6/H-7/H-8/H-9, H-5/H-9, and
H-8/H-10, in combination with HMBC
correlations of H-3/C-1, revealed that 3 is
an iridoidal derivative. HMBC correlation
of a proton at d 3.38 with a carbon at d
100.9 positioned the methoxy group at
C-1. Acid hydrolysis of 3 afforded a
D-glucose identified by comparison with
reference compound in terms of TLC and
specific rotation. The anomeric proton at d
Compound 2 had the molecular for-
mula C15H20O3 deduced from its HR-EI-
MS at m/z 248.1406 [M]þ, requiring 6
degrees of unsaturation. The IR spectrum
indicated the presence of OH (3425 cm21
and a,b-unsaturated ketone (1629 cm21
)
)
functionalities. Fifteen carbon signals in
the 13C NMR and DEPT spectra were
attributed to two methyl, four methylene
including one oxygenated methylene, two
methine including an olefinic one, and six
quaternary carbons (four olefinic ones, one
carbonyl group, and one sp3 quaternary
carbon). These data suggested that 2 is an
analog of 1. Compared to 1, compound 2
has a ketone group positioned at C-9 and a
hydroxyl attached to C-6. This conclusion
was supported by the HMBC correlations
of H-1/C-10, C-9, H-8/C-6, C-7,C-9, C-10,
O
OH
1
10
9
13
7
3
5
OH
OH
OH
11
14
12
15
1
2
O
11
O
OH
O
H
4'
O
7
3
O
5
1'
HO
1'
11
9
O
O
H
HO
8
OH
1
3
5
10
7
9
O
OH
1
H
O
O
O
1''
10
HO
HO
OH
3
4
Figure 1. The structures of compounds 1–4.

1182
L.-H. Zeng et al.
4.20 (d, 7.8 Hz) indicated a b-configur-
ation glucose. HMBC correlation of H-
10/C-11 suggested the linkage of aglycone
and glucose. The relative configuration of
3 was determined by the ROESY spec-
trum, which showed correlations of H3-
10/H-1, H-9, H-9/H-4, H-11/H-5, and H-
1/H-8 indicative of a-form of H-1, H-4,
and H-9, and b-form of H-5 and H-8. This
is also in accordance with the observation
of the split pattern of H-1 (d, 1.0) and H-9
(brdd, 8.7, 6.8). Hence, the structure of 3
was established as shown in Figure 1, with
a trivial name jasminoid C.
was thus identified as shown in Figure 1,
and named as jasminoid D.
The known compounds were identified
as (1S ,5S ,10aR )-1-[(80S ,8a0R )-80,8a0-
*
*
*
*
*
dimethyl-40-oxo-10,40,60,70,80,8a0-hexahy-
dronaphthalen-20-yl]-4-hydroxy-1,4,5,10a-
tetramethyl-1,2,3,4,5,6,7,9,10,10a-decahy-
droanthracen-9-one (5) [7], tetraol (6) [8],
oleside 7-(tetraol-(500)-ester, 11-methyl
ester (7) [8], oleside 7,11-methyl ester (8)
[9], oleside 11-methyl ester (9) [10], a-
asarone (11) [11], and 2,3-dihydroxypro-
pyl-9-octadecenoate (12) [12], respect-
ively, by comparison with the literature
data.
Compound 4 had the molecular for-
mula C21H32O11 from the HR-EI-MS at m/z
460.1964 [M]þ, 13C NMR, and DEPT
spectra. The most NMR data of 4 were
similar to those of compound 8, which is a
seco-iridoidal derivative. The difference
was that one methyl ester in 8 was replaced
by one butyl ester in 4. This conclusion was
readily confirmed by 1H–1H COSY corre-
lations of H-10/H-20/H-30/H-40, and HMBC
correlations of H-10/C-7 (Figure 2). The
glucosyl moiety was identified as D-
glucose by acid hydrolysis of 4 followed
by TLC comparison with reference com-
pound and optical rotation determination.
The glucose was attached to C-1 by the
observed HMBC correlation of H-100/C-1.
The anomeric proton at d 4.78 (d, 7.8)
suggested a b-configuration glucose.
ROESY correlation of H-1/H-6 indicated
that they are spatially vicinal. Compound 4
3. Experimental
3.1 General experimental procedures
Optical rotations were measured with a
Jasco-20C polarimeter (Jasco, Hachioji,
Tokyo, Japan). IR spectra were obtained on
a Bio-Rad FTS-135 (Bio-Rad, Richmond,
Canada) with KBr pellets. UV spectra were
measured on a Shimadzu UV-210A spec-
trophotometer (Shimadzu, Kyoto, Japan).
NMR spectra were obtained on a Bruker
DRX-500 MHz or a Bruker AV-400 MHz
spectrometer (Bruker Corporation, Swit-
zerland) with TMS as an internal standard.
EI-MS spectra were determined using a VG
Autospec-3000 spectrometer (VG, Man-
chester, England). ESI-MS and HR-ESI-
MS spectra were determined using an API
QSTAR Pulsar 1 spectrometer (Applied
Biosystems/MDS Sciex, Foster City, CA,
USA). Silica gel (200–300 mesh, Qingdao
Marine Chemical Co. Ltd, Qingdao,
China), RP-18 gel (40–63 mm; Daiso Co.,
Osaka, Japan), MCI gel CHP 20P (Mitsu-
bishi, Tokyo, Japan), and Sephadex LH-20
(Amersham Biosciences, Uppsala, Swe-
den) were used for column chromatography
(CC).
O
O
O
H
O
H
O
O
O
OH
OH
OH
O
4
2
HO
HO
HMBC
ROESY
OH
3.2 Plant material
The roots of J. sambac were collected
from jasmine cultivation base of Nan-
Figure 2. Selected HMBC ( ! ) and
COSY(—) correlations of 2 and 4.

Journal of Asian Natural Products Research
1183
ning, Guangxi Province of China, in July
2007. A voucher specimen (CHYX-0389)
has been deposited at the State Key
Laboratory of Phytochemistry and
Plant Resources in West China of our
institute.
filtration over Sephadex LH-20 (MeOH)
to yield a fraction (570 mg), which was
purified by RP-18 gel (aqueous MeOH:
60–90%) followed by vacuum liquid
chromatography (VLC) over silica gel
(CHCl3/MeOH, 30:1) to afford a mixture
(300 mg). The final purification was carried
out by preparative TLC (CHCl3–Me2CO,
20:1) followed by Sephadex LH-20
(MeOH) filtration, which afforded 5
(4 mg) and 11 (18 mg). Fr. 2.4 (6 g) was
fractionated by RP-18 gel (60–90%) to
yield two fractions. Fr. 2.4.1 (800 mg) was
submitted to VLC over silica gel (pet-
roleum ether/EtOAc, 6:1) to give a
subfraction, which was purified by Sepha-
dex LH-20 (MeOH) to afford 2 (5 mg). Fr.
2.4.2 (300 mg) was purified by the
combination of RP-18, silica gel, and
Sephadex LH-20 CC to yield 1 (16 mg).
Fr. 3 (203 g) was divided into five parts over
silica gel CC eluting with EtOAc–MeOH
3.3 Extraction and isolation
The air-dried and powdered roots of
J. sambac (15 kg) were refluxed with 95%
EtOH (3 £ 50 liters). The extracts were
combined and concentrated to give a crude
extract (1.0 kg), which was suspended in
H2O and successively partitioned by
petroleum ether, EtOAc, and n-BuOH.
The latter two parts were combined (400 g)
and were divided into four fractions by a
gradient CHCl3–MeOH. Fr. 2 (30 g) was
passed through an MCI gel CHP 20P
column eluting with gradient aqueous
MeOH (60–90%) to give five fractions.
Fr. 2.2 (4.6 g) was submitted to gel
Table 1. 1H and 13C NMR spectral data of 1 and 2 (d in ppm, J in Hz).
1a
2b
c
dH
c
d
d
No.
dC
dH
dC
1a
1b
2a
2b
3a
3b
4
5
6
7
8
2.81 (dd, 17.7, 6.1)
2.42 (dd, 17.7, 4.7)
1.83 (m)
1.72 (overlap)
1.72 (overlap)
23.8 (CH2)
17.2 (CH2)
30.6 (CH2)
2.40 (ddd, 18.6, 7.6, 1.8)
2.24 (m)
1.84 (m)
1.73 (m)
1.69 (m)
21.9 (CH2)
16.9 (CH2)
31.4 (CH2)
1.58 (m)
3.08 (m)
3.05 (m)
30.2 (CH)
142.4 (qC)
123.9 (qC)
139.6 (qC)
112.9 (CH)
153.2 (qC)
122.7 (qC)
152.6 (qC)
111.1 (CH2)
29.2 (CH)
166.4 (qC)
72.1 (qC)
165.5 (qC)
125.7 (CH)
188.4 (qC)
130.8 (qC)
148.2 (qC)
117.5 (CH2)
6.42 (s)
6.05 (s)
9
10
11
12a
12b
13a
13b
14
15
5.43 (dd, 4.2, 1.9)
4.83 (dd, 4.2, 1.9)
4.11 (brs)
5.53 (m)
5.51 (m)
4.40 (d, 14.6)
4.25 (d, 14.6)
1.52 (s)
65.8 (CH2)
65.5 (CH2)
2.12 (s)
1.14 (d, 7.0)
14.7 (CH3)
21.0 (CH3)
27.8 (CH3)
21.2 (CH3)
1.28 (d, 7.0)
a Acetone-d6; b Methanol-d4; c 1H (400 MHz) and 13C (100 MHz); d 1H (600 MHz) and 13C (150 MHz).

1184
L.-H. Zeng et al.
(5:1), of which, Fr. 3.1(13 g) was passed
through an MCI gel CHP 20P column
(aqueous MeOH, 40–90%) to give a
subfraction (8 g), which was purified by
Sephadex LH-20 (MeOH) and RP-18 CC
(aqueous MeOH, 40–70%) to afford 6
(13 mg). Fr. 3.5 (82 g) was fractionated by
MCI gel CHP 20P (40–90%) to give four
subfractions. Fr. 3.5.4 (26 g) was fractio-
nated by Sephadex LH-20 (MeOH) and
RP-18 CC (aqueous MeOH, 40–55%) to
give a mixture (90 mg), which was
submitted to VLC (EtOAc–MeOH, 20:1)
on silica gel to give 3 (22 mg). In the same
manner, compounds 4 (15 mg) and 10
(6 mg) were purified from Fr. 3.5.5 (32 g).
Fr. 4 was divided into three parts (Fr. 4.1–
4.3) by silica gel CC (EtOAc–MeOH, 5:1).
Fr. 4.1 (40 g) was fractionated into three
portions (Fr. 4.1.1–4.1.3) by MCI gel CHP
20P (aqueous MeOH, 40–90%). Fr. 4.1.3
(13 g) was purified by a combination of
Sephadex LH-20 (MeOH), RP-18 CC
(aqueous MeOH, 40–80%) followed by
VLC (CHCl3/MeOH, 10:1) on silica gel to
give 7 (10 mg). Fr. 4.3 (34 g) was submitted
to MCI gel CHP 20P (aqueous MeOH, 40–
90%) followed by a combination of RP-18,
Sephadex LH-20 CC (MeOH) and VLC
(CHCl3/MeOH, 12:1) over silica gel to
yield 8 (80 mg) and 9 (140 mg).
Table 2. 1H (400 MHz) and 13C (100 MHz) NMR spectral data of 3 and 4 (d in ppm, J in Hz).
3a 4a
No.
dH
dC
dH
dC
1
4.56 (d, 1.0)
100.9 (CH)
62.1 (CH2)
5.90 (s)
7.50 (s)
95.1 (CH)
155.1 (CH)
3a
3b
4
3.76 (dd, 11.0, 4.6)
3.57 (t, 11.0)
1.78 (m)
2.02 (overlap)
1.72 (m)
1.64 (m)
38.1 (CH)
37.3 (CH)
29.2 (CH2)
109.4 (qC)
31.9 (CH)
41.2 (CH2)
5
3.97 (overlap)
2.69 (dd, 14.1, 4.5)
2.44 (dd, 14.1, 9.3)
6a
6b
7a
7b
8
2.02 (overlap)
1.22 (m)
32.7 (CH2)
173.3 (qC)
2.02 (overlap)
1.43 (brdd, 8.7, 6.8)
1.03 (d, 6.3)
3.98 (dd, 10.0, 3.5)
3.27 (overlap)
4.20 (d, 7.8)
34.9 (CH)
51.8 (CH)
20.2 (CH3)
71.6 (CH2)
6.08 (q, 7.1)
124.7 (CH)
130.6 (qC)
14.1 (CH3)
168.7 (qC)
9
10
11a
11b
10a
10b
20
1.71 (dd, 7.1, 0.9)
105.1 (CH)
4.06 (m)
65.7 (CH2)
3.97 (overlap)
1.58 (m)
1.37 (m)
3.18 (dd, 9.0, 7.8)
3.38 (m)
3.27 (overlap)
3.27 (overlap)
3.88 (dd, 11.8, 1.9)
3.69 (dd, 11.8, 5.4)
75.1 (CH)
78.0 (CH)
71.7 (CH)
77.9 (CH)
62.7 (CH2)
31.7 (CH2)
20.2 (CH2)
13.6 (CH3)
30
40
0.92 (t, 7.4)
50
600a
600b
1
4.78 (d, 7.8)
100.8 (CH)
74.8 (CH)
78.4 (CH)
71.5 (CH)
77.9 (CH)
62.8 (CH2)
200
3.28 (overlap)
3.28 (overlap)
3.28 (overlap)
3.37 (m)
3.86 (dd, 11.9, 1.9)
3.64 (dd, 11.9, 5.5)
3.69 (s)
300
400
500
600a
600b
O-Me
3.38 (s)
55.2 (CH3)
51.9 (CH3)
a Methanol-d4.

Journal of Asian Natural Products Research
3.3.5 Acid hydrolysis of 4
1185
3.3.1 (þ)-Jasminoid A (1)
25
White solids. ½aꢀD þ 19.4 (c ¼ 0.28
A solution of 4 (5 mg) in 2N HCl (6 ml)
was heated in a H2O bath at 708 for 6 h.
After cooling, the mixture was neutralized
with NaHCO3 and extracted with EtOAc.
The optical rotation determination of H2O
layer containing pure glucose suggested
MeOH); UV (MeOH) lmax (log 1): 284
(2.62), 207 (3.67); IR (KBr) nmax 3425,
2924, 2869, 1630, 1418, 1325, 1255,
1037 cm21; H (400 MHz) and 13C NMR
1
(100 MHz) spectral data, see Table 1. ESI-
MS (negative): m/z 232 [M–H]2 ; HR-
ESI-MS (negative): m/z 231.1384
[M–H]2 (calcd for C15H19O2, 231.1385).
23
the D-form of glucose (½aꢀD ¼ þ33.2
(c ¼ 0.13, H2O)).
Acknowledgements
This work was financially supported by the
Project of Natural Compound Library Con-
struction from Chinese Academy of Sciences
(KSCX2-EW-R-15) and National Natural
Science Foundation of China (No. 81060361).
3.3.2 Jasminoid B (2)
23
White solids. ½aꢀD 2 48.9 (c ¼ 0.08,
MeOH); UV (MeOH) lmax (log 1): 244
(3.11), 202 (3.21) nm; IR (KBr) nmax
3425, 2925, 1629, 1451, 1391, 1056 cm21
1H (600 MHz) and 13C NMR (150 MHz)
spectral data, see Table 1. EI-MS: m/z 248
[M]þ. HR-EI-MS: m/z 248.1406 [M]þ
(calcd for C15H20O3, 248.1412).
:
.
Note
1. These authors contributed equally to this
work.
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3.3.3 Jasminoid C (3)
25
White solids. ½aꢀD 2 18.7 (c ¼ 0.39,
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2951, 2923, 2871, 1630, 1461, 1378, 1066,
1
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23
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1
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