Biochemical Systematics and Ecology 87 (2019) 103962

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Biochemical Systematics and Ecology

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A new phenylpropanoid glycoside from the bark of Streblus ilicifolius (Vidal) T

Corner
Gaorong Zhang, Lili Hao, Dexiong Zhou, Wei Liu, Chenguo Li, Shanshan Su, Xia Xu,
Xishan Huang∗, Jun Li∗∗
State Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University,
Guilin, 541004, PR China

ARTICLE INFO ABSTRACT

Keywords: A new compound, pheglycoside A (1), along with four known aromatic glycosides (2-5) and three known lignan
Streblus ilicifolius (Vidal) Corner glycosides (6–8) were isolated from Streblus ilicifolius (Vidal) Corner. The structure of compound 1 was de-
Moraceae termined by spectral analyses, including HRESIMS, 1D, and 2D NMR (COSY, HSQC, and HMBC) experiments.
Pheglycoside A The absolute configuration of compound 1 was determined using the CD spectrum and experiment data. From
Icariside E5
the present investigation, all these compounds were isolated for the first time from S. ilicifolius. It is interesting
Chemotaxonomy
that phenylpropanoid glycoside and aromatic glycosides are reported for the first time in the genus Streblus. The
chemotaxonomic significance of these compounds was summarized.

1. Subject and source 3. Present study

The genus Streblus (Moraceae) is widely distributing in South China
and South Asia (Zhang et al., 1998). Some plants of the genus Streblus,
such as Streblus asper Lour., Streblus indicus (Bur.) Corner, contain fla-
vonoids, coumarins, lignans and other compounds, and are widely used
as the medicinal plant in Southern China, Malaysia, Philippines and
Thailand (Gaitonde et al., 1964; Taweechaisupapong et al., 2000; Li
et al., 2008, 2012; Pongpan et al., 1982; Sripanidkulchai et al., 2009;
Chen et al., 2012; Suresh Kumar et al., 2015; Khare et al., 1962;
Phutdhawong et al., 2004; He et al., 2017a; Wongkham et al., 2001).
S. ilicifolius (Vidal) Corner belongs to the genus of Streblus,
Moraceae. The bark of S. ilicifolius was collected in August 2018 from
Lingshui, a city of Hainan province, China, and was authenticated by
Prof. Guodong Li, College of Traditional Chinese Medicine, Yunnan
University of Chinese Medicine. A voucher specimen (No.
ZFC201903014e) was deposited in the Natural Products Laboratory of
Guangxi Normal University.
2. Previous work
Until now, no reports are found about chemical constituents of S.
ilicifolius.
The air-dried bark (20 kg) of S. ilicifolius was powdered and refluxed
with 75% EtOH (2 h × 3) to generate a crude extract (1.5 kg). The
crude extract was suspended in water and successively partitioned with
different solvents into EtOAc (Fraction A, 523 g) and n-BuOH (Fraction
B, 374 g) fractions. Fraction B was applied to a silica gel CC, eluting
with CH2Cl2–MeOH (100:0–0:100, v/v) to give seven fractions (Fr. B-1 -
Fr. B-7). Fr. B-3 (29 g) was subjected to RP-C18 CC using a gradient of
MeOH–H2O (from 5% to 100% MeOH) to afford eight fractions (Fr. B-3-
1 - Fr. B-3-8). Fr. B-3-3 (4.0 g) was chromatographed over Sephadex LH-
20 CC, eluting with MeOH–H2O (5:90–80:20) to give eight fractions (Fr.
B-3-3-1 - Fr. B-3-3-8). Fr. B-3-3-1 was purified by semi-preparative
HPLC (MeOH–H2O, 20:80, v/v) to yield compounds 3 (6.6 mg) and 5
(3.8 mg). Fr. B-3-3-4 was isolated using RP-C18 CC eluting with
MeOH–H2O (30:70, v/v), then purified by Sephadex LH-20 CC with
MeOH as a solvent to afford compound 6 (4.6 mg). Fr. B-3-3-6 (111 mg)
was purified by semi-preparative HPLC (MeOH–H2O, 43:54, v/v) to
yield compound 1 (7 mg). Fr. B-3-3-8 (79.8 mg) was subjected to
Sephadex LH-20 CC and then purified by semi-preparative HPLC
(MeOH–H2O, 72:28, v/v) to yield compound 8 (6 mg). Fr. B-3-4 was
separated by the semi-preparative HPLC eluted with a gradient of
MeOH–H2O (20:80 → 50:50, v/v) to give six fractions (Fr. B-3-4-1 - Fr.

∗
Corresponding author.
∗∗
Corresponding author.
E-mail addresses: huangxishan13@foxmail.com (X. Huang), lijun9593@gxnu.edu.cn (J. Li).

https://doi.org/10.1016/j.bse.2019.103962
Received 4 September 2019; Received in revised form 28 October 2019; Accepted 2 November 2019
0305-1978/ © 2019 Elsevier Ltd. All rights reserved.
G. Zhang, et al. Biochemical Systematics and Ecology 87 (2019) 103962

Table 1
1
H NMR (400 MHz) and13C NMR (100 MHz) spectroscopic data of compound 1
in methanol-d4.
Position δH (J = Hz) δC

1 137.7
2 7.43 (m) 127.7
3 7.32 (m) 129.6
4 7.25 (m) 129.0
5 7.32 (m) 129.6
6 7.43 (m) 127.7
7 6.74 (d, 16.0) 135.3
8 6.16 (d, 16.0, 8.0) 128.5
9 4.91 (m) 75.9
10 2.83 (dd, 15.1, 7.5), 42.0
2.69 (dd, 15.1, 6.1)
11 173.2
12 3.68 (s) 52.2
1′ 4.37 (dd, 7.8) 100.9
2′ 3.28 (m) 75.0
3′ 3.22 (d, 8.2) 78.1
4′ 3.32 (m) 71.7
5′ 3.22 (m, 8.2) 78.0
6′ 3.66 (dd, 11.9, 2.2), 62.9
3.88 (dd, 11.9)

Fig. 1. Chemical structures of compounds isolated from the bark of S. ilicifolius.

B-3-4-6). Fr. B-3-4-2 was further isolated using semi-preparative HPLC

eluting with MeOH–H2O (20:80, v/v) to yield compounds 4 (3.5 mg)
and 7 (5.1 mg). Fr. B-3-4-5 was separated by Sephadex LH-20 CC
(MeOH) and preparative HPLC (MeOH–H2O, 20:80, v/v) to afford
compound 2 (7.5 mg).
In this study, one new compound (1), along with seven known
compounds (2–8) were isolated from n-BuOH extract of S. ilicifolius. The
seven known compounds were identified as 3,4,5-trimethoxyphenyl-
(6′-O-galloyl)-O-β-D-glucopyranoside (2) (Verotta et al., 2001), 2,4,6- Fig. 2. Key 1H–1H COSY and HMBC correlations of compound 1.
trimethoxyphenyl-1-O-β-D-glycoside (3) (Chang et al., 2013), 4-hy-
droxy-3-methoxyphenyl-1-O-β-D-(5-O-syringoyl)-apiofuranosyl-(1–2)-
In the 1H–1H COSY spectrum, correlations from H-7 (δH 6.74) to H-8
β-D-glucopyranoside (4) (Silva et al., 2007), 3,4,5-trimethoxyphenyl-1-
(δH 6.16), H-8 (δH 6.16) to H-9 (δH 4.91) and H-9 (δH 4.91) to H-10 (δH
O-β-apiofuranosyl(1"→6′)-β-glucopyranoside (5) (Kanchanapoom et al.,
2.83, 2.68) were observed, which concluded a fragment of
2002), icariside E5 (6) (Lee et al., 2009), seco-isolariciresinol 9-O-β-
–CH]CH–CH(O)–CH2– (Fig. 2). In the HMBC spectrum, correlations
glucopyranoside (7) (Ohashi et al., 1994) and (+)-lyonirenisol-3α-O-β-
from H-7 to C-1 and C-2/6 were observed, indicating C-1 was connected
D-glucopyranoside (8) (Strack et al., 1989) by comparing their NMR
to C-7. The HMBC data revealed correlations from H-12 to C-11 and
spectroscopic data with the published values (Fig. 1).
from H-10 to C-11, suggesting the methoxy and C-10 were connected to
Compound 1 was isolated as a pale yellow oil. The compound gave
C-11 (Fig. 2). The HMBC spectrum (Fig. 2) showed a correlation from
the molecular formula C18H24O8 as deduced from the NMR data and the
H-1′ to C-9, which suggested that the glucosyl group of compound 1
HRESIMS (positive) ion at m/z 391.13568 [M + Na] + (calc. for
was connected to C-9. Thus, the planar of 1 was identified.
C18H24O8Na, 391.13689). The 1H NMR spectrum of 1 (Table 1) had
The absolute configuration of compound 1 was determined by
signals for a mono-substituted benzene ring at δH 7.43 (H-2 and H-6),
comparing the calculated CD spectrum with experimental ECD (Fig. 3).
7.32 (H-3 and H-5) and 7.25 (H-4), one trans double bond protons at δH
The recorded CD spectrum of 1 was consistent with the calculated ECD
6.74 (1H, d, J = 16.0 Hz), 6.16 (1H, dd, J = 16.0, 8.0 Hz), one methoxy
at δH 3.68 (3H, s), two methylene, one at δH 2.83 (1H, dd, J = 15.1,
7.5 Hz) and δH 2.69 (1H, dd, J = 15.1, 6.1 Hz), another at δH 3.88 (dd,
J = 11.9 Hz) and 3.66 (dd, J = 11.9, 2.2 Hz), one methine at δH 4.91
(1H, m). Meanwhile, the 1H NMR spectrum revealed the signals of one
glycosyl moiety, an anomeric proton signal at δH 4.37 (1H, d,
J = 7.8 Hz). The 13C NMR spectrum exhibits 18 carbon signals, in-
cluding six aromatic carbons (δC 129.6, 129.6, 129.0, 137.7, 127.7,
127.7), a couple of olefinic carbons (δC 135.3, 128.5), one carbonyl
carbon (δC 173.2), an oxygen-substituted methine carbon (δC 75.9), one
methoxy carbon (δC 52.2), one methylene carbon (δc 42.0) and one
glycosyl moiety (δC 100.9, 78.1, 78.0, 75.0, 71.7, 62.9). The 1H NMR
and 13C NMR data of 1 were similar to those of piperwallioside B and
piperwallioside C (Shi et al., 2015). Furthermore, comparison of the
coupling constant of an anomeric proton at δH 4.37 (J = 7.8 Hz) and
optical rotation data with those of piperwallioside B and piperwallio- Fig. 3. Experimental ECD spectrum of 1 (red) and calculated ECD spectra of
(9S)-1 (blue) and (9R)-1 (black). (For interpretation of the references to color in
side C suggested that the glycosyl moiety of compound 1 was β-D-
this figure legend, the reader is referred to the Web version of this article.)
glucopyranoside (Shi et al., 2015).

2
G. Zhang, et al.
curve for (9S)-1. Thus, the structure of 1 was established and named as
pheglycoside A (Fig. 1).
Pheglycoside A (1): pale yellow oil; - 70.01 (c 2.3, MeOH); CD (c
0.2, MeOH): 265 (- 13); UVMeOH max nm (log ε): 280 (2.43), 210.3
(0.60); HRESIMS (positive) m/z: 391.13568 [M + Na]+ (calc. for
C18H24O8Na, 391.13689). NMR spectra: see Table 1.
4. Chemotaxonomic significance
The Streblus genus is one of the genera in the Moraceae family
(Zhang et al., 1998). A number of studies on the chemical constituents
of this genus have been reported these years (Li et al., 2012, 2013; He
et al., 2016, 2017b; Zhao et al., 1999; Ren et al., 2017; Singh et al.,
1994; Chawal et al., 1990; Fiebig et al., 1985).
In our present research, eight compounds, including one new phe-
nylpropanoid glycoside (1), four known aromatic glycosides (2-5), and
three known lignan glycoside derivatives (6–8) were isolated from S.
ilicifolius for the first time (Fig. 1). Compound 1 is phenylpropanoid
glycoside, which was isolated for the first time from this genus, sug-
gesting their specialty in this plant. It is reported that some other genus
also can produce this type of compounds (Bai et al., 2019; Lin et al.,
2019). It is interesting that phenylpropanoid glycoside and aromatic
glycosides are reported for the first time from the genus of Streblus.
These results suggest the chemical taxonomic significance to study the
genus of Streblus. These compounds isolated from this genus help us to
understand the significance of chemotaxonomic from chemical com-
position diversity.
It is reported that some plants of the Streblus genus contain large
amounts of lignan derivatives. These lignan glycosides (compounds 6,
7, and 8) were isolated for the first time from this genus. Therefore, the
existence of similar lignans suggested their closely chemotaxonomic
relationships among S. asper and S. indicus.
All the compounds (1–8) were isolated from this plant for the first
time. The result extends the knowledge about the phytochemical con-
stituents of the genus Streblus and shows the presence of uncommon
metabolites encountered in Streblus, especially for the plant S. ilicifolius.
Declaration of competing interest
The authors declared that they have no conflicts of interest to this
work.
Acknowledgments
Authors (J. Li. and X.S. Huang) acknowledge the following grants
for funding this project: National Natural Science Foundation of China
(21662004); Natural Science Foundation of Guangxi Province, China
(2018JJD140035, 2018JJA140613, and 2017GXNSFBA1980083);
Open Research Fund Program of the Key Laboratory for the Chemistry
and Molecular Engineering of Medicinal Resources, China
(CMEMR2019-A1).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.bse.2019.103962.
Biochemical Systematics and Ecology 87 (2019) 103962
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