Three new glycosides from Hylocereus undatus

Article abstract of DOI:10.1080/10286020.2011.586944

Three new glycosides, undatusides A-C (1-3), and 11 known compounds (4-14) were isolated from the flowers of Hylocereus undatus. Their structures were elucidated on the basis of spectroscopic data and chemical method.

Full text of DOI:10.1080/10286020.2011.586944

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Three new glycosides from Hylocereus
undatus
Xin Wu a b , Ying Wang b c , Xiao-Jun Huang b c , Chun-Lin Fan b c
,
Guo-Cai Wang b c , Xiao-Qi Zhang b c , Qin-Wen Zhang d & Wen-Cai
Ye a b c
a Department of Phytochemistry , China Pharmaceutical
University , Nanjing, 210009, China
b Institute of Traditional Chinese Medicine and Natural Products,
College of Pharmacy, Jinan University , Guangzhou, 510632, China
c JNU-HKUST Joint Laboratory for Neuroscience and Innovative
Drug Research , Jinan University , Guangzhou, 510632, China
d Institute of Chinese Medical Sciences, University of Macau ,
Macau, China
Published online: 13 Jul 2011.
To cite this article: Xin Wu , Ying Wang , Xiao-Jun Huang , Chun-Lin Fan , Guo-Cai Wang , Xiao-
Qi Zhang , Qin-Wen Zhang & Wen-Cai Ye (2011) Three new glycosides from Hylocereus undatus ,
Journal of Asian Natural Products Research, 13:8, 728-733, DOI: 10.1080/10286020.2011.586944
To link to this article: http://dx.doi.org/10.1080/10286020.2011.586944
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Journal of Asian Natural Products Research
Vol. 13, No. 8, August 2011, 728–733
Three new glycosides from Hylocereus undatus
Xin Wuab†, Ying Wangbc†, Xiao-Jun Huangbc, Chun-Lin Fanbc, Guo-Cai Wangbc,
Xiao-Qi Zhangbc, Qin-Wen Zhangd and Wen-Cai Yeabc
*
aDepartment of Phytochemistry, China Pharmaceutical University, Nanjing 210009, China;
bInstitute of Traditional Chinese Medicine and Natural Products, College of Pharmacy, Jinan
University, Guangzhou 510632, China; JNU-HKUST Joint Laboratory for Neuroscience and
c
d
Innovative Drug Research, Jinan University, Guangzhou 510632, China; Institute of Chinese
Medical Sciences, University of Macau, Macau, China
(Received 1 April 2011; final version received 6 May 2011)
Three new glycosides, undatusides A–C (1–3), and 11 known compounds (4–14)
were isolated from the flowers of Hylocereus undatus. Their structures were elucidated
on the basis of spectroscopic data and chemical method.
Keywords: Hylocereus undatus; Cactaceae; undatusides A–C
1. Introduction
(4–14) (Figure 1). Herein, we report the
isolation and structural elucidation of the
three new compounds.
The plant Hylocereus undatus (Cactaceae)
is widely distributed in the tropical areas of
Africa, south America, and south Asia. The
fruits of Hylocereus species, known as
pitaya or dragon fruit, can be consumed
freshly or processed as ingredient in juice,
jams, or ice cream. In the southern China,
the flowers of H. undatus have been used as
food and folk medicine for the treatment of
hyperactivity, cough, tuberculosis, mumps,
bronchitis, and cervical lymph node tuber-
culosis for a long time. Previous phyto-
chemical studies on this plant had resulted
in the isolation of two triterpenes with
microvascular protective activity [1]. As a
part of the program to assess the chemical
and biological diversity of the medicinal
plants in the southern China, we carried out
the chemical investigation of the flowers of
H. undatus, which led to the isolation of
three new glycosides, undatusides A–C
(1–3), as well as 11 known compounds
2. Results and discussion
The molecular formula of 1 was established
as C19H26O10 by the pseudo-molecular ion
in its HR-ESI-MS at m/z 437.1423
[M þ Na]þ. The UV spectrum of 1 showed
the absorption maxima at 208 and 251 nm.
The IR spectrum implied the presence
of hydroxyl (3325 cm21), carbonyl
(1723 cm21), and aromatic ring (1637 and
1
1455cm21). The H NMR spectrum of 1
indicated the presence of five aromatic
protons [dH 7.39 2 7.25 (5H, m)], three
methylenes [dH 4.85 (1H, d, J ¼ 12.0Hz),
4.62 (1H, d, J ¼ 12.0Hz), 2.77 (1H, d,
J ¼ 15.6Hz),2.72(1H,d,J ¼ 15.6Hz), and
2.67 (2H, s)], and a methyl [dH 1.38 (3H, s)].
1
Furthermore, the H NMR spectrum dis-
played the signals due to an anomeric
proton [dH 4.36 (1H, d, J ¼ 7.5 Hz)] and a
*Corresponding author. Email: chywc@yahoo.com.cn
†These authors contributed equally to this work.
ISSN 1028-6020 print/ISSN 1477-2213 online
q 2011 Taylor & Francis
DOI: 10.1080/10286020.2011.586944
http://www.informaworld.com

Journal of Asian Natural Products Research
729
HO
HO
RO
5''
HO
O
5''
O
6'
O
O
O
4
HO
3''
3''
O
4''
4''
1''
O
6'
1''
2''
OR2
2''
1
O
2
5
3
R1O
O
2
4
3
O
O
1'
1'
O
HO
HO
1
HO
HO
1
7
OH
OH
6
8
4
5
6
R1 = H
R
2 = CH3
R
R
1 = CH3 R2 = H
1
2
R = H
R = CH3
3
1 = R2 = H
R
1
OH
HO
HO
O
O
O
HO
O
O
O
HO
HO
HO
HO
OH
OH
OH
8
7
OH
OH
9
R = OH
OH
10 R = H
OH
HO
O
O
HO
O
OR
OCH3
O
O
OH
O
OH
O
O
OH
O
HO
HO
HO
O
O
HO
O
HO
HO
HO
HO
O
OH
HO
HO
HO
13 R = CH3
14 R = H
12
11
Figure 1. Chemical structures of compounds 1–14.
hydroxymethyl group [dH 4.48 (1H, dd,
J ¼ 11.8, 2.0 Hz) and 4.23 (1H, dd,
J ¼ 11.8, 5.7 Hz)], as well as proton signals
in the region dH 3.46 2 3.24 (4H, over-
lapped), suggesting the presence of a sugar
moiety. Acid hydrolysis of 1 afforded
D-glucose, which was identified by gas
chromatography (GC) analysis using
an authentic sample as reference. The
b-configuration of D-glucose was deter-
[2], indicating that 1 possessed the same
substructure, which was further supported
by the HMBC correlations between H2-200
[dH 2.77 (1H, d, J ¼ 15.6Hz) and 2.72 (1H,
d, J ¼ 15.6Hz)] and C-400 (dC 45.9)/300-CH3
(dC 27.7), between H-400 [dH 2.67 (2H, s)]
and C-200 (dC 46.3)/300-CH3 (dC 27.7), as
well as between 300-CH3 [dH 1.38 (3H, s)]
andC-200 (dC 46.3)/C-400 (dC 45.9)(Figure2).
S-configuration for the C-300 of the HMG
moiety was assumed because naturally
occurring HMG esters are formed via the
acylation of the hydroxyl group with (S)-
HMG-CoA [3,4]. Comparison of the NMR
spectral data assigned to 1b with those of
benzyl-b-D-glucopyranoside (7) suggested
that they were very similar, except for the
obvious downfield shift of C-60 and upfield
shift of C-50, suggesting that the HMG
moiety (1a) was esterified with the hydroxyl
group at C-60 of the glucose moiety.
Moreover, the HMBC correlations between
H-60 (dH 4.48 and 4.23) and C-100 (dC 172.4)
3
mined based on the JH1,H2 coupling
constant (J ¼ 7.5 Hz) of the anomeric
proton. The 13C NMR and DEPT spectra
of 1 revealed the presence of 19 carbon
signals, including two carbonyl groups, a
monosubstituted benzene ring, as well as a
b-D-glucopyranosyl unit. With the aid of
1H–1H COSY, HSQC, and HMBC exper-
iments, all the 1H and 13C NMR signals of 1
were assigned as shown in Table 1.
The 1H and 13C NMR signals of 1
assigned to 1a were very similar to those of
3-hydroxy-3-methylglutaryl (HMG) moiety

730
X. Wu et al.
d
d
d
d
d
d

Journal of Asian Natural Products Research
731
J ¼ 7.3 Hz); dC 37.1], indicating the pre-
senceofphenethylunitin3insteadofbenzyl
moiety. With the aid of 1H–1H COSY,
HSQC, and HMBC experiments, all the 1H
and 13C NMR signals of 3 were assigned as
shown in Table 1. Furthermore, the HMBC
correlations between H-10 (dH 4.30) and C-1
(dC 71.8), as well as between H2-60 (dH 4.44
and 4.20) and C-100 (dC 172.4), suggested
that the phenethyl and HMG units were
connected to the C-10 and C-60 positions of
glucose, respectively. Based on the above
results, the structure of 3 was established as
phenethyl-1-O-[60-O-(S)-300-hydroxy-300-
methylglutaryl]-b-D-glucopyranoside and
named as undatuside C.
HO
4''
CH3
HO
2''
O
O
1''
1a
1b
O
6'
O
O
HO
1'
HO
1
3
OH
1
Figure 2. Key HMBC correlations of 1.
confirmed the above deducement. There-
fore, the structure of 1 was elucidated
as benzyl-1-O-[60-O-(S)-300-hydroxy-300-
methylglutaryl]-b-D-glucopyranoside and
named as undatuside A.
In addition, the 11 known compounds
were elucidated as (R)-(2)-citramalic acid
1-methyl ester (4) [5], (R)-(2)-citramalic
acid 4-methyl ester (5) [6], (R)-(2)-
citramalic acid (6) [7], benzyl-b-D-gluco-
pyranoside (7) [8,9], phenethyl-b-D-gluco-
pyranoside (8) [10], dihydroquercetin (9)
[11], dihydrokaempferol (10) [12], kaemp-
ferol 3-neohesperidoside (11) [13], quer-
cetin 3-O-b-D-rutinoside (12) [14], trans-
3,4-dimethoxycinnamic acid (13) [15], and
trans-ferulic acid (14) [16], respectively,
by comparison of their physical and
spectroscopic data with those reported in
the literature.
The molecular formula of 2 was
established as C20H28O10 by the pseudo-
molecular ion in its HR-ESI-MS at m/z
451.1584 [M þ Na]þ. The UV spectrum of
2 showed the absorption maxima at 211
and 258 nm. The IR spectrum implied the
presence of hydroxyl (3377 cm21), carbo-
nyl (1729 cm21), and aromatic ring (1687
and 1452 cm21). Acid hydrolysis of 2 also
afforded D-glucose. The 1H and 13C NMR
spectral data of 2 were very similar to those
of 1 except for the presence of methyl ester
[dH 3.63 (3H, s); dC 173.1 and 51.9] instead
of the aliphatic acid group. Thus, the
structure of 2 was assigned as benzyl-1-O-
[60-O-(S)-300-hydroxy-300-methyl-500-meth-
oxyglutaryl]-b-D-glucopyranoside and
named as undatuside B.
3. Experimental
3.1 General experimental procedures
Optical rotation values were measured on a
JASCO P-1020 digital polarimeter at room
temperature. UV spectra were recorded on
a JASCO V-550 UV/VIS spectropho-
tometer. IR spectra were measured on a
JASCO FT/IR-480 plus Fourier transform
infrared spectrometer with KBr pellets. 1D
and 2D NMR spectra were recorded on
Bruker AV-300 spectrometer. HR-ESI-MS
data were acquired using an Agilent 6210
LC/MSD TOF mass spectrometer. ESI-MS
data were determined on a Finnigan
LCQ Advantage spectrometer. Column
chromatographies (CC) were carried out
The molecular formula of 3 was
determined to be C20H28O10 by the
pseudo-molecular ion in its HR-ESI-MS at
m/z 451.1584 [M þ Na]þ. Similar to 1 and
2, the IR spectrum of 3 showed the presence
of hydroxyl (3331 cm21), carbonyl
(1723 cm21), and aromatic ring (1637,
1455 cm21). Acid hydrolysis of 3 also
1
afforded D-glucose. The H and 13C NMR
spectral data of 3 were closely similar to
those of 1 except for the presence of an
additional methylene [dH 2.90 (2H, d,

732
X. Wu et al.
using silica gel (200–300 mesh, Qingdao
Haiyang Chemical Group Corporation,
Qingdao, China) and Sephadex LH-20
(Pharmacia Biotech AB, Uppsala, Swe-
den). TLC analysis was performed on
precoated silica gel GF254 plates (Yantai
Chemical Industrial Institute, Yantai,
China). Analytical high-performance
liquid chromatography (HPLC) was car-
ried out on a Dionex chromatography
equipped with a P680 pump, a PDA-100
photodiode array detector, and a Cosmosil
5C18-MS-II reversed-phase column
(4.6 mm £ 250 mm, 5.0 mm, Nacalai
Tesque, Kyoto, Japan). Preparative HPLC
was carried out on a Varian instrument
equipped with a Prostar 215 pump, a
Prostar 325 UV/VIS detector, and a
Cosmosil 5C18-MS-II reversed-phase col-
umn (20 mm £ 250 mm, 5.0 mm, Nacalai
Tesque, Kyoto, Japan).
(100:0 ! 0:100) as eluent to give four
fractions (Fr. 1–4). Fr. 2 (30 g) was
separated by silica gel column using
CHCl3–acetone (100:0 ! 0:100) as eluent
to yield three subfractions (Fr. 2a–2c). Fr.
2a (14 g) was subjected to preparative
HPLC [CH3OH–H2O (40: 60)] to give
compounds 4 (188mg), 5 (131mg), and 6
(336mg). Fr. 2b (11 g) was re-separated by
Sephadex LH-20 column (CH3OH) and
preparative HPLC [CH3OH-H2O (25: 75)]
to yield compounds 1 (84 mg), 2 (23 mg), 3
(34 mg), 7 (1170 mg), 8 (129 mg), 9
(12 mg), 10 (14 mg), 11 (20 mg), 12
(21 mg), 13 (150 mg), and 14 (30 mg),
respectively.
3.3.1 Compound 1
Colorless oil: ½aꢀ2D1 234.8 (c 0.1, CH3OH);
UV (CH3OH) lmax (log1) 208 (3.88), 251
(2.58)nm; IR (KBr): nmax 3325, 2932,
2886, 1724, 1637, 1455, 1383, 1318, 1210,
1160, 1079, 1046, 1019, 905, 751,
3.2 Plant material
1
The flowers of H. undatus were collected in
Zhaoqing city, Guangdong Province of
China, in February 2010, and authenticated
by Prof. Guang-Xiong Zhou (Institute of
Traditional Chinese Medicine & Natural
Products, Jinan University). A voucher
specimen (No. 20100215) has been depos-
ited in the Institute of Traditional Chinese
Medicine & Natural Products, Jinan Uni-
versity, Guangzhou, China.
700 cm21; H and 13C NMR spectral data,
see Table 1; HR-ESI-MS m/z 437.1423
[M þ Na]þ (calcd for C19H26O10Na,
437.1418).
3.3.2 Compound 2
Colorless oil: ½aꢀ2D1 229.8 (c 0.2, CH3OH);
UV (CH3OH) lmax (log1) 211 (3.74), 258
(2.52)nm; IR (KBr): nmax 3377, 2944, 2874,
1729, 1687, 1452, 1354, 1323, 1209, 1158,
1078, 1049, 1019, 912, 742, 700 cm21; 1H
and 13C NMR spectral data, see Table 1;
HR-ESI-MS m/z 451.1584 [M þ Na]þ
(calcd for C20H28O10Na, 451.1575).
3.3 Extraction and isolation
The air-dried flowers of H. undatus (15 kg)
were powdered and extracted with 95%
(V/V) EtOH at room temperature, and the
solution was evaporated under vacuum to
yield a residue (5700 g). The crude EtOH
extract was subsequently suspended in
distilled water and partitioned successively
with petroleum ether, ethyl acetate, and
n-butanol, respectively. After removing
the solvent, the ethyl acetate extract (90 g)
was subjected to silica gel CC using
gradient mixtures of CHCl3 –CH3OH
3.3.3 Compound 3
21
Colorless oil: ½aꢀD 212.9 (c 0.3,
CH3OH); UV (CH3OH) lmax (log 1) 212
(3.59), 258 (2.38) nm; IR (KBr): nmax
3331, 2938, 2881, 1723, 1637, 1455, 1381,
1318, 1202, 1158, 1085, 1017, 908, 748,
700 cm21; 1H and 13C NMR spectral data,
see Table 1; HR-ESI-MS m/z 451.1584

Journal of Asian Natural Products Research
733
[M þ Na]þ (calcd for C20H28O10Na,
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).
451.1575).
3.4 Acid hydrolysis and GC analysis of
1–3
Each solution of compounds 1–3 (each
1.5 mg) was heated in an ampoule with
1.5 ml of 2 N HCl (CH3OH-H2O, 1:1) at
958C for 2 h. The solution was evaporated
with a stream of N2. The reaction mixture
was dissolved in H2O and extracted with
CHCl3. The aqueous layer was evaporated
to give a residue. Then, 2 ml of anhydrous
pyridine and 3 mg of L-cysteine methyl
ester hydrochloride were added to the
residue, and the reaction mixture was
heated at 608C for 2 h. The solution was
concentrated to dryness with N2. Further-
more, N-(trimethylsilyl)imidazole (0.2 ml)
was slowly added into the reaction mixture
and then kept at 608C for 1 h. Finally, H2O
(1 ml) was added to the solution to stop the
reaction, and the aqueous layer was
extracted with hexane (2 ml). The organic
layer was analyzed using GC under the
following conditions: column: HP-1701
(0.25 mm £ 30 mm, 0.5 mm), detector:
FID, column temperature: 200–2508C
(5 8C/min), detector temperature: 2808C,
injector temperature: 2508C, and carrier
gas: N2. The standard D-glucose and L-
glucose were subjected to the same
reaction and GC analysis under the above
conditions [tR (min): 32.231 (D-glucose),
34.863 (L-glucose)]. As a result, D-glucose
[tR (min): 32.185] was detected from the
hydrolyzates of 1–3, respectively.
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Acknowledgements
This work was supported financially by the
Program for Changjiang Scholars and Innovative
Research Team in University (No. IRT0965), the