Natural Product Research

Formerly Natural Product Letters

ISSN: 1478-6419 (Print) 1478-6427 (Online) Journal homepage: http://www.tandfonline.com/loi/gnpl20

A new depsidone derivative from the leaves of

Garcinia polyantha

Alain Meli Lannang, Denis Kehdinga Sema, Simplice J. N. Tatsimo, V. F.

Tsague Tankeu, Hycienth F. Tegha, Jean Duplex Wansi, Yoshihito Shiono &
Norbert Sewald

To cite this article: Alain Meli Lannang, Denis Kehdinga Sema, Simplice J. N. Tatsimo, V. F.
Tsague Tankeu, Hycienth F. Tegha, Jean Duplex Wansi, Yoshihito Shiono & Norbert Sewald
(2017): A new depsidone derivative from the leaves of Garcinia polyantha, Natural Product
Research, DOI: 10.1080/14786419.2017.1378201

To link to this article: http://dx.doi.org/10.1080/14786419.2017.1378201

View supplementary material

Published online: 20 Sep 2017.

Submit your article to this journal

View related articles

View Crossmark data

Full Terms & Conditions of access and use can be found at

http://www.tandfonline.com/action/journalInformation?journalCode=gnpl20

Download by: [University of Sussex Library] Date: 21 September 2017, At: 00:17
 Natural Product Research, 2017
https://doi.org/10.1080/14786419.2017.1378201

A new depsidone derivative from the leaves of Garcinia

polyantha
Alain Meli Lannanga,b,c, Denis Kehdinga Semaa, Simplice J. N. Tatsimoa,
V. F. Tsague Tankeua, Hycienth F. Teghaa, Jean Duplex Wansid, Yoshihito Shionoc and
Norbert Sewaldb
a
Department of Chemistry, Higher Teachers’ Training College, University of Maroua, Maroua, Cameroon;
b
Faculty of Agriculture, Department of Food, Life, and Environmental Science, Yamagata University, Tsuruoka,
Downloaded by [University of Sussex Library] at 00:17 21 September 2017

Japan; cDepartment of Chemistry, Organic and Bioorganic Chemistry, Bielefeld University, Bielefeld, Germany;
d
Faculty of Sciences, Department of Chemistry, University of Douala, Douala, Cameroon

ABSTRACT ARTICLE HISTORY

One new depsidone, polyanthadepsidone A (1), together with four Received 14 June 2017
known compounds were isolated from the dichloromethane extract Accepted 25 August 2017
of the leaves of Garcinia polyantha. The structures of all compounds
KEYWORDS
were determined by comprehensive analyses of their 1D and 2D NMR Garcinia polyantha;
and EI mass spectral data. All the isolates exhibited suppressive effect Guttiferae; depsidone;
on phagocytosis response upon activation with serum opsonised oxidative burst
zymosan in the IC50 range of 4.5–23.80 μM, tested in vitro for oxidative
burst studies of whole blood.

1. Introduction
Garcinia, one of the biggest genera of the family Guttiferae, has been found to be a rich
source of xanthones (Bennett and Lee 1989), biflavonoids, benzophenones (Waterman and
Hussain 1983), prenylated depsidone (Xu et al. 2000; Ha et al. 2012; Sukandar et al. 2016),
biphenyl derivatives (Sukandar et al. 2016) as well as triterpenoids and steroids (Nguyen and
Harrison 2000) and many others. Phenolic constituents from Garcinia species have been
reported to possess various biological activities, including antibacterial (Suksamrarn et al.
CONTACT  Alain Meli Lannang  alainmeli@yahoo.com
 Supplemental data for this article can be accessed at https://doi.org/10.1080/14786419.2017.1378201.
© 2017 Informa UK Limited, trading as Taylor & Francis Group
 2   A. M. LANNANG ET AL.

2003; Hay et al. 2004), cytotoxic (Shadid et al. 2007; Meli Lannang et al. 2014), suppressive
effect on phagocytosis response upon activation with serum opsonised zymosan (Ngoupayo
et al. 2009) and prooxidant (Wu et al. 2008) activities. They also display inhibitory activity
against α-glucosidase, glycation (Fouotsa et al. 2012), and HIV (Gustafson et al. 1992). Garcinia
polyantha is well kown to contain xanthones, benzophenones and terpenoids with antiox-
ydant, citotoxicity activities and enzyme inhibition (Meli Lannang et al. 2005, 2014; Louh
et al. 2008). In line of our search for new and/or active substances from medicinal plants, we
report here the chemical constituents of G. polyantha, an endemic plant growing in Mount
Kala, Central Region of Cameroon.

2.  Results and discussion

Downloaded by [University of Sussex Library] at 00:17 21 September 2017

The dicchlromethane extract of the leaves of G. polyantha was partitioned with petroleum
ether and ethyl acetate. The petroleum ether extract was subjected to successive flash and
column chromatography over silica gel and Sephadex to obtain a new depsidone derivative
named polyanthadepsidone A (1) and four other known compounds (2–5) identified as
1,7-dihydroxy-4-methoxyxanthone (2) (Kijjoa et al. 1998), 1,5-dihydroxyxanthone (3) (Meli
Lannang et al. 2005), Polyanxanthone A (4) (Louh et al. 2008), Polyanxanthone B (5) (Louh
et al. 2008), (Figure 1).
Compound 1 was isolated as pale yellow oil, and the molecular formula was determined
as C18H18O7, by High-Resolution Mass Spectrometry (HR-MS). The IR spectrum showed
absorption bands due to hydroxyl group and lactone carbonyl group at 3541, 3305 (br) and
1675, 1280 cm−1, respectively (Sukandar et al. 2016). The proton and carbon spectra coupled
with DEPT showed the signal of 18 carbons, including 1 O-methyl, 4 methyl and 13 quaternary
carbons (including 6 oxygenated). This entire result together with HMBC, HMQC and COSY
showed a signal of O-methyl group at δH 3.79 (3H, s) and δC 60.4; four methyl groups at δH

OH
O
10
8
9 O 11
O OH O OH
11a 1 HO
O 7 2
6 O
5
OH
4
3
O O
OH
OMe OH
1 2 3

O O O O

O O O
O O
4 5

Figure 1. Structure of isolated compounds.

 NATURAL PRODUCT RESEARCH   3

2.32 (3H, s), 2.44 (3H, s), 2.51 (3H, s), 2.52 (3H, s) and δC 10.2, 10.7, 14.7 and 18.5 respectively;
a lactone carbonyl group at δC 162.7. HMBC showed long-range correlations between
hydroxyl group at δH 6.19 (OH-3) with quaternary aromatic carbons at δC 153.4 (C-3), 114.4
(C-4) and 118.8 (C-2), while the methyl at δH 2.44 (CH3-4) showed long-range correlations
with quaternary aromatic carbon at δC 114.4 and two quaternary oxygenated aromatic car-
bons at δC 153.4 (C-3) and 159.5 (C-4a). The methyl at δH 2.52 (CH3-1) showed long-range
correlations with quaternary aromatic carbons at δC 138.1 (C-1), 115.3 (C-11a) and 118.8
(C-2). All these data indicated that one part of compound 1 is substituted with three methyl
and one hydroxyl groups. In the other part, HMBC between the O-methyl group at δH 3.79
(O-CH3-7) showed long-range correlation with the carbon at δC 151.9 (C-7), while the methyl
at δH 2.32 (CH3-8) showed long-range correlation with δC 122.3 (C-8), 142.0 (C-9) and 151.9
(C-7). These data showed that this part of the compound is substituted with O-methyl, methyl
Downloaded by [University of Sussex Library] at 00:17 21 September 2017

and two hydroxyl groups. These analyses were also confirmed by mass fragment ions at m/z
169 [M+ −.C10H9O3] and 214 [M+ − .C9H8O]. As a consequence, we unambiguously attributed
to compound 1 the name polyanthadepsidone A, first depsidone highly methylated from
Garcinia species, usually present as prenylated and/or hydroxylated (Xu et al. 2000; Ha et al.
2012; Sukandar et al. 2016). These are different from lichens and fungus depside (Talontsi
et al. 2013; Leal et al. 2017) because of the presence of hydroxyl group in the position 1 or
9. The biosynthetic pathway of Garcinia depside is still unknown.
Compounds 1–5, were screened over a range of concentrations (3.1–50 μg/mL) for their
oxidative burst inhibitory potential. These compounds were shown to possess inhibitory
activity upon activation with serum opsonised zymosan, which was tested in vitro for oxi-
dative burst studies of whole blood, polymorphoneutrophils (PMNs) and Mononuclear cells
(MNCs). Compounds 3 showed significant effects on the oxidative burst of the whole blood
(IC50 32.9 μM), while compounds 2 and 3 showed inhibition of the oxidative burst of the
PMNs (IC50 21.1 and 8.6 μM, respectively). Compound 2 showed inhibition of the oxidative
burst of the MNCs (IC50 23.8 μM) (Table S1). PMNs and MNCs were activated using two dif-
ferent cell activators: the serum opsonised zymosan and phorbol-12-myristate-13-acetate
(PMA). The tested compounds exhibited a clear suppressive effect on phagocyte oxidative
burst response upon activation with serum opsonised zymosan in a dose-dependent manner
(Figure S6).

3. Experimental
3.1. General
IR spectra were recorded in CHCl3 on a JASCO A-302 IR spectrophotometer. The 1H, 13C, and
2D NMR spectra were recorded on a Bruker AMX-500 spectrometer using (CD3)2CO as solvent.
Homonuclear 1H–1H connectivities were determined by COSY 45° experiment. One-bond
1
H–13C connectivities were determined by HMQC. Two- and three-bond 1H–13C connectivities
were determined by HMBC. Proton chemical shifts are reported in δ (ppm) with reference
to the residual (CD3)2CO signal at δ 2.05, and 13C NMR spectra are referenced to the central
peak of (CD3)2CO at δ 29.84 and 206.26. Coupling constants (J) were measured in Hz. The
EIMS were recorded on a double-focusing mass spectrometer (Varian MAT 311A). HREIMS
were recorded on a JEOL HX 110 mass spectrometer. Column chromatography was carried
out on silica gel 60 (70–230 and 240–300 mesh sizes, E. Merck), and with Sephadex LH-20
 4   A. M. LANNANG ET AL.

(GE Healthcare Europe GmbH) . Preparative thin layer chromatography was done on PTLC
plates (E. Merck, F254). Precoated silica gel TLC plates (E. Merck, F254) were used to check
the purity of compounds, and ceric sulphate spray reagent was used for the visualisation of
compounds by TLC.

3.2.  Plant material

The leaves of G. polyantha were collected in Yaoundé, Center region, Cameroon, in February
2009 and identified by Mr. Victor Nana from Cameroon national Herbarium where a voucher
specimen (21337/SRF/Cam/Mt Kala) has been deposited.

3.3.  Extraction and isolation

Downloaded by [University of Sussex Library] at 00:17 21 September 2017

The dried and powdered leaves of G. polyantha (2.0 kg) was extracted at room temperature
with MeOH (3 × 20 L) for three days. The extract was concentrated and suspended in water
followed by successive partitioning with petroleum ether, dichloromethane, EtOAc and
n-BuOH, respectively. The dichloromethane extract (12.6 g) was separated by silica gel col-
umn chromatography (CC) (10 × 40 cm, 200.0 g) under vacuum using a gradient eluent
mixture of petroleum ether/EtOAc (20 : 1–3 : 1. 3 L each) to afford six fractions (Fr1-Fr6).
Fraction 3 (2.2 g) was subjected to silica gel CC (4 × 30 cm, 20.0 g) under vacuum eluted with
petroleum ether/EtOAc (10 : 1–3 : 1.100 mL each) to give five sub-fractions 3a-3e, and com-
pound 2 (12 mg) was obtained from sub-fraction 3a. Sub-fraction 3b (125.0 mg) was sub-
jected to silica CC (5 × 40 cm, 50.0 g) under vacuum using a gradient eluent mixture of
petroleum ether/EtOAc (20 : 1–3 : 1.50 mL each) to afford compounds 3 (10 mg), 4 (4 mg)
and 5 (3.5 mg). Fraction 4 (20.0 mg) was subjected to Sephadex LH-20 chromatography
eluting with methanol to obtain compound 1 (4.4 mg). The entire isolated compounds were
more than 97% pure.

3.3.1.  Polyanthadepsidone A (1)

Amorphous pale yellow oil showing a purple dark colour under UV light at 365 nm; UV
(MeOH) λmax (logɛ): 205 (3.21), 209 (sh) (3.18), 280 (3.06), 325 (2.81) nm; 242, 363 nm; IR
(CHCl3) νmax: 3541, 3305 (brd), 1675, 1582, 1280, 1150 cm−1; HR-MS found: m/z: 346.1046
(Calcd for 346.1053). 1H NMR (500 MHz, CD3Cl) δ: 2.52 (3H, s, Me-1), 2.51 (3H, s, Me-2), 2.44
(3H, s, Me-4), 2.32 (3H, s, Me-8), 3.79 (3H, s, OMe-7), 6.19 (1H, s, OH-3), 5.32 (2H, s, OH-6 and
OH-9). 13C NMR (125 MHz, CD3Cl) δ: 138.1 (C-1), 118.8 (C-2), 153.4 (C-3), 114.4 (C-4), 159.5
(C-4a), 146.5 (C-5a), 126.7 (C-6), 151.9 (C-7), 122.3 (C-8), 142.0 (C-9), 125.2 (C-9a), 162.7 (C-11),
115.3 (C-11a), 18.5 (Me-1), 14.7 (Me-2), 10.7 (Me-4), 10.2 (Me-8), 60.4 (OMe-7).

3.4.  Chemiluminescence assay for determination of immuno-modulatory activity

A luminol-enhanced chemiluminescence assay was performed, as described by Helfand
et al. (Helfand et al. 1982). In brief, whole blood (diluted 1:200) and neutrophils (1 × 107)
suspended in Hank’s balance salt solution with calcium and magnesium (HBSS+2) were incu-
bated with 50 μL for each test compound at concentrations of 3.1–50 μg/mL for 30 min.
Then, 50 μL (20 mg/mL) of zymosan (Sigma Chemical Co., St. Louis, MO) followed by 50 μL
 NATURAL PRODUCT RESEARCH   5

(7 × 105 M) of luminol (G-9382 Sigma) and then HBSS++ were added to adjust the final volume
to 0.2 mL. HBSS++ was used as a control.

Acknowledgements
AML would like to thank MATSUMAE International Fellowship for a grant in the Department of Food,
Life, and Environmental Science, Faculty of Agriculture, Yamagata University, Tsuruoka, Yamagata and
the Alexander von Humboldt-Stiftung for support through Georg Forster Fellowship for Experienced
Researchers (ID N° 1137675) at the University of Bielefeld (Germany) and the return scholarship.

Disclosure statement
No potential conflict of interest was reported by the authors.
Downloaded by [University of Sussex Library] at 00:17 21 September 2017

Funding
This work was supported by the Alexander von Humboldt-Stiftung [grant number 1137675].

References
Bennett GJ, Lee HH. 1989. Xanthones from the Guttiferae. Phytochemistry. 28:967–998.
Fouotsa H, Lannang AM, Mbazoa CD, Rasheed S, Bishnu PM, Zulfiqar A, Krishna PD, NKengfack AE,
Farzana S, Muhammad IC, et al. 2012. Xanthones inhibitors of α-glucosidase and glycation from
Garcinia nobilis. Phytochem Lett. 56:236–239.
Gustafson KR, Blunt JW, Munro MHG, Fuller RW, McKee TC, Cardellina JH II, McMahon JB, Cragg GM, Boyd
MR. 1992. The guttiferones, HIV-inhibitory benzophenones from Symphonia globulifera, Garcinia
livingstonei, Garcinia ovalifolia and Clusia rosea. Tetrahedron. 48:10093–10102.
Ha LD, Hansen PE, Duus F, Pham HD, Nguyen LHD. 2012. Oliveridepsidones A-D, antioxidant depsidones
from Garcinia oliveri. Magn Reson Chem. 50:242–245.
Hay AE, Helesbeux JJH, Duval O, Labaïed M, Grellier P, Richomme P. 2004. Antimalarial xanthones from
Calophyllum caledonicum and Garcinia vieillardii. Life Sci. 75:3077–3085.
Helfand SL, Werkmeister J, Roder JC. 1982. Chemiluminescence response of human natural killer
cells. I. The relationship between target cell binding, chemiluminescence, and cytolysis. J Exp Med.
156:492–505.
Kijjoa A, Jose M, Gonzalez TG, Pinto MMM, Damas AM, Mondranondra IO, Silva AMS, Herz W. 1998.
Xanthones from cratoxylum maingayi. Phytochemistry. 49:2159–2162.
Meli Lannang A, Komguem J, Tangmouo JG, Lontsi D, Ngounou FN, Ajaz A, Choudhary MI, Rangit R,
Devkota KP, Sondengam BL. 2005. Banganxanthone A and B, two xanthones from the stem barks
of Garcinia polyantha. Phytochemistry. 66:2351–2355.
Meli Lannang A, Tatsimo SJN, Fouotsa H, Dzoyem JP, Saxena AK, Sewald N. 2014. Cytotoxic compounds
from the leaves of Garcinia polyantha. Chem Biodiversity. 11:975–981.
Leal A, Rojas JL, Valencia-Islas NA, Castellanos L. 2017. New β-orcinol depsides from Hypotrachyna
caraccensis, lichen from the Páramo ecosystem and their free radical scavenging activity. Nat Prod
Res. doi:10.1080/14786419.2017.1346639.
Louh GN, Meli Lannang A, Mbazoa CD, Tangmouo JG, Komguem J, Castilho P, Ngounou FN, Qamar N,
Lontsi D, Choudhary MI, et al. 2008. Polyanxanthone A, B and C, three xanthones from the wood
trunk of Garcinia polyantha Oliv. Phytochemistry. 69:1013–1017.
Ngoupayo J, Tabopda TK, Muhammad SA. 2009. Antimicrobial and immunomodulatory properties of
prenylated xanthones from twigs of Garcinia staudtii. Bioorg Med Chem. 17:5688–5695.
Nguyen DLH, Harrison LJ. 2000. Xanthones and triterpenoids from the bark of Garcinia vilersiana.
Phytochemistry. 53:111–114.
 6   A. M. LANNANG ET AL.

Shadid KA, Shaari K, Abas F, Israf DA, Hamzah AS, Syakroni N, Saha K, Lajis NH. 2007. Cytotoxic caged-
polyprenylated xanthonoids and a xanthone from Garcinia cantleyana. Phytochemistry. 68:2537–
2544.
Sukandar ER, Siripong P, Khumkratok S, Tip-pyang S. 2016. New depsidones and xanthone from the
roots of Garcinia schomburgkiana. Fitoterapia. 111:73–77.
Suksamrarn S, Suwannapoch N, Phakhodee W, Thanuhiranlert J, Ratananukul P, Chimnoi N, Suksamrarn
A. 2003. Antimycobacterial activity of prenylated xanthones from the fruits of Garcinia mangostana.
Chem Pharm Bull. 51:857–859.
Talontsi FM, Douanla-Meli C, Laatsch H. 2013. Depsidones from an endophytic fungus Chaetomium
sp. associated with Zanthoxylum leprieurii. Z Naturforsch. 68b: 1259–1264.
Waterman PG, Hussain RA. 1983. Systematic significance of xanthones, benzophenones and biflavonoids
in Garcinia. Biochem Systemat Ecol. 11:21–28.
Wu CC, Lu YH, Wei BL, Yang SC, Won SJ, Lin CN. 2008. Phloroglucinols with prooxidant activity from
Gracinia subelliprica. J Nat Prod. 71:246–250.
Downloaded by [University of Sussex Library] at 00:17 21 September 2017

Xu YJ, Chiang PY, Lai YH, Vittal JJ, Wu XH, Tan BKH, Imiyabir Z, Goh SH. 2000. Cytotoxic prenylated
depsidones from Garcinia parvifolia. J Nat Prod. 63:1361–1363.