Aromatic monoterpenoid glycosides from the seeds of Paeonia ostii

Article abstract of DOI:10.1080/10286020.2017.1307191

Phytochemical investigation into the seeds of Paeonia ostii T. Hong et J. X. Zhang (Paeoniaceae) led to the identification of three new aromatic monoterpenoid glycosides, named paeostisides A–C (1–3), along with one known compound. Their structures were identified by spectroscopic analysis and chemical method.

Full text of DOI:10.1080/10286020.2017.1307191

Journal of Asian Natural Products Research
ISSN: 1028-6020 (Print) 1477-2213 (Online) Journal homepage: http://www.tandfonline.com/loi/ganp20
Aromatic monoterpenoid glycosides from the
seeds of Paeonia ostii
Jun-Jun Qin, Ying-Yi Mao, Jin-Long Li, Yan Guan & Wei-Min Zhao
To cite this article: Jun-Jun Qin, Ying-Yi Mao, Jin-Long Li, Yan Guan & Wei-Min Zhao (2017):
Aromatic monoterpenoid glycosides from the seeds of Paeonia ostii, Journal of Asian Natural
Products Research, DOI: 10.1080/10286020.2017.1307191
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Date: 28 April 2017, At: 23:09

Journal of asian natural Products research, 2017
http://dx.doi.org/10.1080/10286020.2017.1307191
Aromatic monoterpenoid glycosides from the seeds of
Paeonia ostii
Jun-Jun Qina,b§, Ying-Yi Maoc§, Jin-Long Lia,d§, Yan Guanc and Wei-Min Zhaoa
adepartment of natural Product chemistry, shanghai institute of Materia Medica, chinese academy of
sciences, shanghai 201203, china; buniversity of chinese academy of sciences, Beijing 100049, china; cabbot
d
laboratories, anrd, shanghai 200233, china; school of Pharmacy, nantong university, nantong 226001,
china
ABSTRACT
ARTICLE HISTORY
received 30 november 2016
accepted 13 March 2017
Phytochemical investigation into the seeds of Paeonia ostii T. Hong
et J. X. Zhang (Paeoniaceae) led to the identification of three new
aromatic monoterpenoid glycosides, named paeostisides A–C (1–3),
along with one known compound. Their structures were identified by
spectroscopic analysis and chemical method.
KEYWORDS
Paeonia ostii; Paeoniaceae;
monoterpenoid glycoside;
paeostisides a–c
1. Introduction
Paeonia ostii T. Hong et J. X. Zhang (Paeoniaceae) is an ornamental and medicinal plant.
e root barks of P. ostii together with P. suff r uticos a Andr. have been used in traditional
Chinese medicine as Cortex Moutan with heat-clearing, blood circulation promoting, and
blood stasis dissipating effects [1]. e flowers of P. ostii are also used in aromatherapy
with main constituents of (Z)-9-tricosene, ethyl myristate, and germacrone. [2]. e seeds
of P. ostii were found to be rich in unsaturated fatty acids, and have been used as a new
dietary oil source [3]. Previous phytochemical study on the seeds of P. ostii also revealed
the existence of monoterpenoid glycosides, phenolic glycosides, flavonoid glycosides, and
triterpenoids [4–6]. In order to know more about the polar components of the seeds of P.
ostii for the purpose of finding potential application of the oil cake, systematically phy-
tochemical investigation was undertaken. We herein report the isolation and structural
elucidation of three new monoterpenoid glycosides, named paeostisides A–C, along with
one known compound (Figure 1).
CONTACT Wei-Min Zhao
wmzhao@simm.ac.cn; Yan Guan
yan.guan@abbott.com
§these authors contributed equally to this work.
© 2017 informa uK limited, trading as taylor & francis Group

2
J.-J. QIN ET AL.
OH
O
7
6
6''
3
8
OH
OH
4
HO
HO
2
1''
O
OH
O
6
3''
5
5
OH
HO
O
HO
HO
O
1
O
HO
1
3
OH
OH
9
10
OH
OH
1
2
OH
OH
OH
OH
O
O
HO
HO
HO
HO
O
O
OH
OH
OH OH
OH
3
4
Figure 1. structures of compounds 1–4.
2. Results and discussion
Compound 1 was obtained as a white amorphous powder. Its HRESIMS showed a quasi-
molecular ion at m/z 527.1735 [M + Na]+. In its 1H NMR spectrum, two singlet aromatic
proton signals at δH-2 6.98 (s, 1H) and δH-5 6.63 (s, 1H); two terminal olefinic proton signals
at δH-10a 5.31 (br s, 1H) and δH-10b 5.11 (br s, 1H); two anomeric proton signals at δH-1′ 4.86
(d, J = 7.4 Hz, 1H) and δH-1′ 4.35 (d, J = 7.7 Hz, 1H); an oxygenated methylene at δH-9 4.44
(m, 2H); and a tertiary methyl at δH-7 2.20 (s, 3H) were recognized, as well as six aromatic
carbon signals at δC 151.6, 148.9, 129.9, 126.0, 119.7, and 117.1; two olefinic carbons at δC
149.8 and 113.9; two anomeric carbon signals at δC 103.5 and 104.7 in its 13C NMR spec-
trum, suggesting the existence of a 1,3,4,6-tetrasubstituted aromatic ring, a terminal olefinic
function, and two saccharide moieties. HPLC-MS analysis of the hydrolytic product of
compound 1 with appropriate derivatization [7], together with the large coupling constants
of two anomeric proton signals, implied two sugar units as β-D-glucose. e HMBC cor-
relations from H-7 to C-2, C-4; from H-9 to C-6, C-10; from H-10 to C-6, C-9; from H-1′
to C-1; and from H-1″ to C-6′ enabled deduction of the planar structure of 1 as shown in
Figure 2. Its structure was further confirmed by NOE correlation signals between H-5 and
H-9; between H-2 and H-1′ in the NOESY spectrum (Figure 3). erefore, the structure of
1 was characterized as 4,9-dihydroxy-8(10)-ene-thymol-1-O-β-D-glucopyranosyl-(1→6)-
β-D-glucopyranoside, and assigned the trivial name paeostiside A.
e 13C NMR spectra of paeostiside B (2) and paeostiside C (3) revealed identical
saccharide signals to those of the known compound 4,9-dihydroxy-8,10-dehydrothy-
mol-1-O-β-D-glucoside (4) [4], and HPLC-MS analysis of their hydrolysates with appro-
priate derivatization confirmed the existence of D-glucose moiety in their structures. e
molecular formula of 2 was determined to be C16H24O8 based on the sodium adduct ion
at m/z 367.1360 in its HRESIMS. Comparison of the 1H and 13C NMR data indicated that
compound 2 differed from 4 only with the absence of the terminal olefinic function, and the
presence of a secondary methyl (δH 1.18, d, J = 6.6 Hz, 3H; δC 17.4). In the HMBC spectrum
of 2, 1H-13C long-range correlation signals were observed between H-5 and C-8; between

JOURNAL OF ASIAN NATURAL PRODUCTS RESEARCH
3
OH
OH
OH
OH
O
HO
HO
OH
O
OH
O
O
OH
HO
O
HO
HO
HO
HO
O
O
O
HO
OH
OH
OH
OH
OH OH
OH
1H
13C
1
2
3
Figure 2. Key hMBc correlations of compounds 1–3.
OH
H
O
H
H
OH
OH
HO
OH
HO
O
HO
HO
OH
O
O
OH
O
OH
O
HO
O
H
H
O
H
HO
HO
HO
OH
OH
OH
OH OH
OH
1H
1H
OH
1
2
3
Figure 3. Key noesY correlations of compounds 1–3.
H-8 and C-1, C-5, C-9, C-10; between H-9 and C-6, C-10; and between H-10 and C-6, C-9
(Figure 2). Besides, NOE signals were found between H-5 and H-8, H-10 (Figure 3), which
enabled characterization of the structure of 2 as 4,9-dihydroxy-thymol-1-O-β-D-glucopyra-
noside as shown in Figure 1. In comparison with 1H and 13C NMR spectra of 2, the 1H NMR
spectrum of 3 showed another pair of methylene signals at δH 3.79 (dd, J = 10.8, 7.2 Hz,
1H) and δH 3.75 (dd, J = 10.8, 6.1 Hz, 1H), as well as the corresponding carbon signal at δC
64.5 in its 13C NMR spectrum, with the loss of one methyl signal. e HMBC correlations
from H-8 to C-1, C-5; from H-9 to C-6, C-8; and from H-10 to C-6, C-8 (Figure 2), and
the NOE signals between H-2 and H-1′; and between H-5 and H-8 (Figure 3) revealed the
structure of 3 as 4,9,10-trihydroxy-thymol-1-O-β-D-glucopyranoside as shown in Figure 1.
3. Experimental
3.1. General experimental procedures
Optical rotations were obtained on a PerkinElmer 341 polarimeter (PerkinElmer, Waltham,
MA, USA). UV spectra were measured with a Cary 300-Bio UV-Visible spectrometer (Varian,
Palo Alto, CA, USA). IR spectra were recorded on a Nicolet 6700 spectrometer (ermo
Scientific, Waltham, MA, USA). NMR data were obtained using a Varian-MERCURY Plus-
400 (Varian, Palo Alto, CA, USA) or Bruker Advance III 500 (Bruker, Ettlingen, Germany)
spectrometer with TMS as the internal reference. ESIMS analyses were carried out on a
Shimadzu LC-MS-2020 (Shimadzu, Kyoto, Japan) with a Shimadzu SPD-M20 (Shimadzu,
Kyoto, Japan) diode array detector using CNW C18 column (2.1 × 50 mm, 3.5 μm; Anpel
Scientific Instrument Co., Ltd., Shanghai, China). HRESIMS analyses were performed on
a Micromass Ultra Q-TOF mass spectrometer (Waters, Milford, MA, USA). Preparative
HPLC was performed on a Unimicro EasySep TM-1010 binary pump system (Unimicro,
Shanghai, China) with a Unimicro EasySepTM-1010 detector (Unimicro, Shanghai, China)

4
J.-J. QIN ET AL.
using a YMC-Pack ODS-A column (250 × 20 mm, 5 μm; YMC Co., Ltd., Kyoto, Japan) and
a Diol-120-NP (250 × 20 mm, 5 μm; YMC Co., Ltd, Kyoto, Japan). Column chromatography
(CC) was performed with Diol-gel (SMB100-20/45, Chromatorex, Fuji Silysia Chemical,
Ltd., Kasugai, Japan), and C18 reversed-phase (RP-C18) silica gel (150−200 mesh; Merck,
Whitehouse Station, NJ, USA).
3.2. Plant material
e seeds of Paeonia ostii T. Hong et J. X. Zhang were collected in Bozhou, Anhui Province,
China, in July 2014, and a voucher specimen has been identified by Prof. Jigang Han of
Shanghai Chenshan Botanical Garden.
3.3. Extraction and isolation
Air-dried seeds of P. ostii (5 kg) were powdered and percolated with 95% EtOH (3 × 10 L)
at room temperature to afford a crude extract (490 g). e extract was then suspended in
33% MeOH and filtrated, and the supernatant (300 g) was applied to RP-C18 gel CC eluted
with MeOH/H2O (from 3 to 100%, v/v) to yield eight fractions (Fr.1~8). Fr.3 (2.35 g) was
further applied to Diol-120-NP CC with a petroleum ether/ethanol gradient (from 65 to
100%, v/v) as eluent to yield compound 3 (3.9 mg). Fr.4 (5 g) was subjected to Diol column
and eluted with petroleum ether/ethanol (2:1→1:3, v/v) to give 13 subfractions (Fr.41~413).
Fr.46 (450 mg) was purified by preparative HPLC with an eluent of 15% MeOH (MeOH/
H2O, v/v) to yield compounds 1 (5.2 mg) and 2 (3.5 mg). Fr.413 (560 mg) was subjected to
preparative HPLC (MeOH/H2O, 10:90→40:60, v/v) to yield compound 4 (21.6 mg).
3.3.1. Paeostiside A (1)
White amorphous powder; [α]D20 − 28.6 (c 0.07, MeOH); UV (MeOH) λmax nm (log ε) 203
(4.0), 286 (3.0); IR (KBr) νmax 3358, 2922, 2852, 1659, 1632, 1412, 1040 cm−1; for 1H and 13C
NMR (CD3OD) spectroscopic data, see Tables 1 and 2; HRESIMS: m/z 527.1735 [M + Na]+
(calcd for C22H32O13Na, 527.1741).
3.3.2. Paeostiside B (2)
White amorphous powder; [α]D20 − 24.8 (c 0.11, MeOH); UV (MeOH) λmax nm (log ε) 202
(3.9), 282 (2.8); IR (KBr) νmax 3358, 2923, 2852, 1658, 1632, 1412, 1073, 1037 cm−1; for 1H
and 13C NMR (CD3OD) spectroscopic data, see Tables 1 and 2; HRESIMS: m/z 367.1360
[M + Na]+ (calcd for C16H24O8Na, 367.1369).
3.3.3. Paeostiside C (3)
White amorphous powder; [α]D20 − 50.0 (c 0.02, MeOH); UV (MeOH) λmax nm (log ε) 203
(4.4), 283 (3.2); IR (KBr) νmax 3358, 2923, 2852, 1658, 1632, 1410, 1066 cm−1; for 1H and 13C
NMR (CD3OD) spectroscopic data, see Tables 1 and 2; HRESIMS: m/z 383.1320 [M + Na]+
(calcd for C16H24O9Na, 383.1313).
3.4. Hydrolyses of compounds 1–4
Several drops of 2N HCl were added to a solution of 1 (1 mg) in dioxane (1 ml) and the
mixture was stirred at 90 °C for 3 h. e solvent was removed in vacuo, and the L-cysteine

JOURNAL OF ASIAN NATURAL PRODUCTS RESEARCH
5
Table 1. 1h nMr spectral data of compounds 1–4 (500 Mhz, δ in ppm, J in hz, methanol-d4).
Position
1
2
3
4
2
5
7
8
9
6.98, s
6.63, s
2.20, s
6.95, s
6.60, s
2.13, s
6.97, s
6.62, s
2.15, s
6.95, s
6.59, s
2.15, s
3.45–3.47, m
3.60–3.62, m
4.43–4.45, m
4.43–4.45, m
5.31, br s
5.11, br s
4.86, d (7.4)
3.59, dd (10.0, 6.6)
3.51, dd (10.0, 6.0)
1.18, d (6.6), 3h
3.84, dd (10.7, 6.5)
3.59, dd (10.7, 6.0)
3.79, dd (10.8, 7.2)
3.75, dd (10.8, 6.1)
4.71, d (7.3)
3.42–3.44, m
3.32–3.34, m
3.35–3.37, m
3.41–3.43, m
3.87, dd (12.0, 2.2)
3.69, dd (12.0, 4.7)
4.39–4.41, m
4.39–4.41, m
5.29, br s
5.08, br s
4.76, d (7.3)
3.22–3.24, m
3.32–3.34, m
3.33–3.35, m
3.37–3.39, m
3.87, dd (12.0, 1.8)
3.66, dd (12.0, 5.1)
10
1′
2′
3′
4′
5′
6′
4.73, d (7.3)
3.44–3.46, m
3.26–3.28, m
3.28–3.30, m
3.34–3.36, m
3.89, dd (12.3, 1.5)
3.69, dd (12.3, 5.1)
3.43–3.45, m
3.30–3.32, m
3.41–3.43, m
3.60–3.62, m
4.17, dd (11.3, 2.0)
3.59, dd (11.3, 5.8)
4.35, d (7.7)
3.23–3.25, m
3.22–3.24, m
3.28–3.30, m
3.24–3.26, m
3.85, dd (11.8, 2.0)
3.66, dd (11.8, 5.5)
1″
2″
3″
4″
5″
6″
Table 2. 13c nMr spectral data of compounds 1–4 (125 Mhz, methanol-d4).
Position
1
2
3
4
1
2
3
4
5
6
7
148.9
119.7
126.0
151.6
117.1
129.9
16.4
145.0
120.2
124.0
151.9
113.8
133.6
16.1
150.4
121.2
124.6
152.1
114.7
130.5
16.1
149.0
120.0
126.0
151.6
117.0
130.0
16.2
8
9
149.8
65.8
35.2
68.9
43.8
64.8
149.8
65.7
10
1′
2′
3′
4′
5′
6′
1″
2″
3″
4″
5″
6″
113.9
103.5
75.1
78.0
71.4
77.2
70.0
104.7
75.1
78.0
17.4
104.4
75.3
78.3
71.5
78.1
62.7
64.5
105.0
75.2
78.1
71.5
78.1
62.6
113.8
103.8
75.2
78.2
71.5
78.1
62.6
71.6
78.0
62.7
methyl ester hydrochloride in pyridine was added. e reaction mixture was maintained at
60 °C for 1 h, and then o-tolyl isothiocyanate was added to the mixture and heated at 60 °C
for another 1 h [7]. e reaction mixture was subjected to HPLC analysis with a UV detector
(250 nm) at 40 °C characterized with a quasimolecular ion at m/z 447 [M + H]+ using a CNW
C18 column (2.1 × 50 mm, 3.5 μm) eluted with 23% CH3CN-H2O containing 0.2% formic
acid at a flow rate of 0.3 ml/min. Authentic D- and L-glucose and compounds 2–4 were
handled in a same manner. e retention times of the derivatives of sugar standards were

6
J.-J. QIN ET AL.
as follows: D-glucose (6.467 min), L-glucose (5.950 min), while the retention times of those
of compounds 1–4 were at 6.450 min, 6.483 min, 6.500 min, and 6.517 min, respectively.
Supporting information
NMR spectra of compounds 1–4 together with the PDA chromatograms and mass spectra
of the derivatives of hydrolysates of 1–4 are provided.
Acknowledgment
e authors appreciate Dr. Na Shu for her contribution in this study.
Disclosure statement
No potential conflict of interest was reported by the authors.
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[5] P. Liu, Z.Y. Lu, R.X. Deng, X. Liu, D.L. Yang, Y.Q. Niu, and W.P. Yin, Chin. Tradit. Herb. Drugs.
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[7] T. Tanaka, T. Nakashima, T. Ueda, K. Tomii, and I. Kouno, Chem. Pharm. Bull. 55, 900 (2007).