A new xanthone glycoside from Pyrrosia sheareri

Article abstract of DOI:10.1080/14786419.2018.1514398

A new xanthone glycoside, 3,5,7,8-tetramethoxyxanthone-1-O-β-D-glucopyranoside (1), along with five known compounds, mangiferin (2), kaempferol (3), quercetin (4), chlorogenic acid (5) and diploptene (6), was isolated from the whole plants of Pyrrosia sheareri (Bak.) Ching. The structure of compound 1 was established on the basis of extensive spectroscopic analyses and chemical methods.

Full text of DOI:10.1080/14786419.2018.1514398

Natural Product Research
Formerly Natural Product Letters
ISSN: 1478-6419 (Print) 1478-6427 (Online) Journal homepage: http://www.tandfonline.com/loi/gnpl20
A new xanthone glycoside from Pyrrosia sheareri
Kang He, Lin-Lin Fan, Tian-Tai Wu & Jiang Du
To cite this article: Kang He, Lin-Lin Fan, Tian-Tai Wu & Jiang Du (2018): A
new xanthone glycoside from Pyrrosiaꢀsheareri, Natural Product Research, DOI:
10.1080/14786419.2018.1514398
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NATURAL PRODUCT RESEARCH
https://doi.org/10.1080/14786419.2018.1514398
A new xanthone glycoside from Pyrrosia sheareri
Kang He, Lin-Lin Fan, Tian-Tai Wu and Jiang Du
The Key Laboratory of Miao Medicine of Guizhou Province, Guiyang College of Traditional Chinese
Medicine, Guiyang, China
ABSTRACT
ARTICLE HISTORY
Received 31 May 2018
Accepted 17 August 2018
A new xanthone glycoside, 3,5,7,8-tetramethoxyxanthone-1-O-b-D-
glucopyranoside (1), along with five known compounds, mangi-
ferin (2), kaempferol (3), quercetin (4), chlorogenic acid (5) and
diploptene (6), was isolated from the whole plants of Pyrrosia
sheareri (Bak.) Ching. The structure of compound 1 was estab-
lished on the basis of extensive spectroscopic analyses and chem-
ical methods.
KEYWORDS
Pyrrosia sheareri (Bak.)
Ching; xanthone glycoside;
3,5,7,8-tetramethoxyxan-
thone-1-O-b-D-
glucopyranoside
1. Introduction
The genus Pyrrosia (Polypodiaceae) comprises approximately 100 species that are
mainly distributed in subtropical regions. There are approximately 37 species of this
genus in China (ECFC 1988). Previous phytochemical investigations on this genus have
afforded various types of compounds including flavonoids, xanthones, triterpenoids,
organic acids and essential oils. (Fu et al. 2017; Xin et al. 2016; Chen et al. 2015; Wang
et al. 2006, 2003; Yang et al. 2003; Yang et al. 2003; Yamashita et al. 1998a, 1998b;
Zheng et al. 1998; Masuda et al. 1997; Han et al. 1984). The antibacterial, anti-
nociceptive, immunosuppressive and antioxidant activities of the extracts of this genus
have been confirmed. (Song et al. 2017; Lim et al. 2014; Jia et al. 2011; Hsu et al.
2008). Pyrrosia sheareri (Bak.) Ching is documented in the Chinese Pharmacopoeia for
the treatment of swelling, urocystitis, urinary calculus, bloody urine, cough, bronchitis,
etc. (NPC 2000) and has also been used to cure infection and diarrhoea in some
CONTACT Jiang Du
dujiang2017@sina.com
Supplemental data for this article can be accessed at https://doi.org/10.1080/14786419.2018.1514398.
ß 2018 Informa UK Limited, trading as Taylor & Francis Group

2
K. HE ET AL.
regions of Guizhou Province, China (ICMGP 1992). However, its chemical constituents
and bioactivities are seldom reported (Joshi et al. 2010). In this study, a new xanthone
glycoside, 3,5,7,8-tetramethoxyxanthone-1-O-b-D-glucopyranoside (1) (Figure 1), along
with five known compounds, was isolated from the whole plants of Pyrrosia sheareri
(Bak.) Ching. We herein report the isolation, structural elucidation and preliminary
chemotaxonomic significance of compound 1.
2. Results and discussion
Compound 1, obtained as a yellow powder, was found to have the molecular formula
C23H26O12 from its HRESIMS data at m/z 529.1103 [M þ Cl]– (calcd 529.1112), corre-
sponding to eleven degrees of unsaturation. The IR spectrum of compound 1 showed
absorption bands for hydroxyl groups (3395 cmꢀ1), aromatic rings (1652, 1629, 1580
cmꢀ1) and ether bonds (1097, 1078, 1060 cmꢀ1). The UV spectrum of compound 1 in
methanol suggested that it was a xanthone derivative with absorption maxima at 201,
247, 298, and 366 nm. Acid hydrolysis of compound 1 with 5% HCl yielded glucose.
The 13C NMR and DEPT spectra of 1 exhibited 23 carbon signals corresponding to ten
quaternary carbons, eight methines, one methylene and four methoxy groups, and of
these carbon resonances, 13 were attributed to a xanthone skeleton and 6 were attrib-
uted to the glucose. The two meta-coupled proton signals [dH 7.27 (1H, d, J = 2.2 Hz,
1
H-2) and 6.78 (1H, d, J = 2.2 Hz, H-4)] observed in the H NMR spectrum in combin-
ation with the correlations of H-2/C-4 (dC 95.9) and C-8b (dC 108.6), H-4/C-2 (dC 101.9)
and C-8b, H-10 [dH 5.54 (1H, d, J = 7.6 Hz)]/C-1 (dC 161.0) and MeO [dH 3.71 (3H, s)]/C-3
(dC 164.9) in the HMBC spectrum suggested that the glucosyl group and a methoxy
group were attached to C-1 and C-3, respectively. The other methoxy groups were
positioned at C-5 (dC 149.4), C-7 (dC 144.3) and C-8 (dC 141.2) by comparing the experi-
mental spectroscopic data with those of 8-hydroxy-1,2,4,6-tetramethoxyxanthone
(Mahendran et al. 2013), and this assignment was also supported by the single aro-
1
matic proton signal [dH 7.14 (1H, s, H-6)] revealed in H NMR spectrum and the HMBC
correlations of H-6/C-4b (dC 140.1) and C-8, MeO [dH 4.10 (3H, s)]/C-8, MeO [dH 3.94
(3H, s)]/C-7 and MeO [dH 3.86 (3H, s)]/C-5. Therefore, the structure of 1 was established
as 3,5,7,8-tetramethoxyxanthone-1-O-b-D-glucopyranoside.
Additionally, five known compounds were isolated and determined to be mangi-
ferin (2) (Wang et al. 2003), kaempferol (3) (Ren et al. 2005), quercetin (4) (Ren et al.
2005), chlorogenic acid (5) (Li and Yu 2011) and diploptene (6) (Wang et al. 2003) by
comparison with the spectroscopic data given in the corresponding references.
Figure 1. Structure of compound 1.

NATURAL PRODUCT RESEARCH
3
Xanthones are distributed in a number of higher plants as well as in fungi and
lichens (Ruan et al. 2017, Tan and Liu 1995). The main xanthone in Pyrrosia is the
C-glycoside mangiferin (Cui et al. 2016). The new xanthone O-glycoside, 3,5,7,8-
tetramethoxyxanthone-1-O-b-D-glucopyranoside (1), is isolated for the first time
from the genus Pyrrosia. This compound may be considered as a fingerprint for P.
sheareri to differentiate it from the other species within the Pyrrosia.
3. Experimental
3.1. Apparatus and reagents
Optical rotations were obtained on a JASCO model 1020 polarimeter (Horiba,
Tokyo, Japan). UV spectra were taken on a Shimadzu UV-2401PC spectrophotometer
(Shimadzu, Kyoto, Japan). IR (KBr) spectra were acquired on a Bio-Rad FTS-135 spectrom-
eter (Bio-Rad, Hercules, California, USA). 1D and 2D NMR spectra were recorded on
Bruker AM-400 spectrometers with TMS as an internal standard (Bruker, Bremerhaven,
Germany). Mass spectra were collected on a Waters AutoSpec Premier P776 instrument
(Waters, USA). Silica gel (200–300 mesh) for column chromatography and TLC plates
(GF254) were obtained from Qingdao Marine Chemical Company (Marine, Qingdao,
China). Sephadex LH-20 (20–150 lm) for chromatography was purchased from
Pharmacia Fine Chemical Co. Ltd. (Pharmacia, Uppsala, Sweden). Fractions were visual-
ized by heating silica gel plates after spraying with 10% H2SO4 in EtOH.
3.2. Plant material
The whole plants of P sheareri (Bak.) Ching were collected from Daozhen County, Guizhou
Province, China, in July 2014. The plant was identified by Prof. Jun-Hua Zhao, College
of Pharmacy, Guiyang College of Traditional Chinese Medicine. A voucher specimen
(No. 140730) was deposited at the Key Laboratory of Miao Medicine of Guizhou Province.
3.3. Extraction and isolation
The air-dried and powdered whole plants of P sheareri (Bak.) Ching (2.1 kg) were
extracted with 90% EtOH (10 L) under reflux three times for 1 h each time. The com-
bined extracts (130 g) were concentrated and suspended in H2O (1 L). The suspension
was extracted with AcOEt. The AcOEt layer provided 22 g of residue, which was sub-
jected to silica gel column chromatography (Si CC) eluted with CHCl3/MeOH
(100:0!6:4) to yield 7 fractions (Frs. A ꢀ G). Fr. B (1.6 g) was subjected to Si CC eluted
with petroleum ether/AcOEt (9:1!1:1) to afford Frs. B1 ꢀ B3. Fr. B2 (830 mg) was
chromatographed over silica gel eluting with petroleum ether/Me2CO (9:1!1:1) to
afford compound 6 (76 mg). Fr. D (1.2 g) was subjected to a Sephadex LH-20 column
(CHCl3/MeOH =1:1) and further purified by Si CC with a gradient eluent of petroleum
ether/Me2CO (9:1!6:4) to provide compound 5 (194 mg). Fr. E (1.3 g) was first sub-
jected to Si CC with a gradient eluent of CHCl3/MeOH (95:5!9:1) and then purified on
a Sephadex LH-20 column (CHCl3/MeOH =1:1) to provide compounds 3 (6 mg) and 4
(9 mg). Compounds 1 (7 mg) and 2 (230 mg) were isolated from Fr. F (2.8 g) by

4
K. HE ET AL.
column chromatography over silica gel (CHCl3/MeOH, 95:5!1:1) and then Sephadex
LH-20 (CHCl3/MeOH =1:1).
3.4. Acid hydrolysis of compound 1
Compound 1 (3 mg) was dissolved in MeOH (1.0 mL) and 10% HCl (1.0 mL) solution
and hydrolysed under reflux for 2 h. The hydrolysate was allowed to cool, diluted with
2 mL of H2O, and extracted with AcOEt (4 mL) 3 times. The aqueous layer was neutral-
ized with aqueous Ba(OH)2 and concentrated in vacuo to give a residue that was
found to contain glucose based on comparison with an authentic sample (BuOH/
AcOEt/H2O 4:1:5, upper layer, Rf 0.45; PhOH/H2O 4:1, Rf 0.50) on PC by spraying with a
phthalic acid-aniline reagent (1.66 g phthalic acid and 0.93 g aniline dissolved in 100
mL of H2O/sat. BuOH), followed by heating. The residue was purified by column chro-
matograph over silica gel (AcOEt/MeOH, 3:2) and identified to be D-glucose based on
the [a]D value ([a]24D: þ29.5, c 0.11, H2O).
3,5,7,8-Tetramethoxyxanthone-1-O-b-D-glucopyranoside (1): Yellow amorphous pow-
der; [a]21D: –11.5 (c 4.63, MeOH); HR-ESI-MS m/z: 529.1103 [M þ Cl]– (calcd for
C23H26O12Cl: 529.1112); UV (MeOH): kmax 201.0, 298.0, 366.5 nm; IR (KBr) ꢀmaxcmꢀ1: 3395,
1
1652, 1629, 1580, 1486, 1430, 1292, 1203, 1097, 1078, 974; H NMR (400 MHz, C5D5N):
7.27 (1H, d, J = 2.2 Hz, H-2), 7.14 (1H, s, H-6), 6.78 (1H, d, J = 2.2 Hz, H-4), 5.54 (1H, d, J =
7.6 Hz, H-10), 4.63 (1H, brd, J = 11.0 Hz, H-60a), 4.49 (1H, dd, J = 8.7, 7.6 Hz, H-20), 4.40
(1H, m, H-30), 4.37 (1H, m, H-60b), 4.31 (1H, t, J = 9.4 Hz, H-40), 4.19 (1H, m, H-50), 4.10
(3H, s, OMe-8), 3.94 (3H, s, OMe-7), 3.86 (3H, s, OMe-5), 3.71 (3H, s, OMe-3); 13C NMR (100
MHz, C5D5N): 175.5 (s, C-9), 164.9 (s, C-3), 161.0 (s, C-1), 158.0 (s, C-4a), 149.4 (s, C-5),
144.3 (s, C-7), 141.2 (s, C-8), 140.1 (s, C-4b), 119.0 (s, C-8a), 108.6 (s, C-8b), 105.2 (d, C-10),
104.8 (d, C-6), 101.9 (d, C-2), 95.9 (d, C-4), 79.3 (d, C-50), 77.9 (d, C-30), 71.5 (d, C-40), 75.1
(d, C-20), 63.0 (t, C-60a), 62.0 (q, OMe-8), 57.7 (q, OMe-7), 56.6 (q, OMe-5), 56.0 (q, OMe-3).
4. Conclusion
Six compounds were isolated from the whole plants of Pyrrosia sheareri (Bak.) Ching.,
and they were elucidated as 3,5,7,8-tetramethoxyxanthone-1-O-b-D-glucopyranoside
(1), mangiferin (2), kaempferol (3), quercetin (4), chlorogenic acid (5) and diploptene
(6). Compound 1, a new xanthone O-glycoside, may be considered as a fingerprint for
P. sheareri to differentiate it from other species within the Pyrrosia. Compounds 3, 4
and 5 were isolated from P. sheareri for the first time.
Disclosure statement
No potential conflict of interest was reported by the authors.
Funding
This work was financially supported by the Science and Technology Foundation of Guizhou
Province [grant number
J (2013) 2071], the Science and Technology Foundation of
Administration of Traditional Chinese Medicine of Guizhou Province [grant number qzyy-2014-

NATURAL PRODUCT RESEARCH
5
087], and the Youth Science and Technology Talent Project of Guizhou Province [grant number
(2017) 5618].
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