Polycyclic polyprenylated acylphloroglucinols and biphenyl derivatives from the roots of Garcinia nuntasaenii Ngerns. & Suddee
Graphical abstract
Previously undescribed polycyclic polyprenylated acylphloroglucinols (garcinuntins A−C), biphenyls (garcinuntabiphenyls A−C), and a lanostane triterpene (garcinuntine), together with thirteen known compounds were isolated from the roots of Garcinia nuntasaenii Ngerns. & Suddee (Clusiaceae). Anti-HIV activity and cytotoxicity of the isolated compounds were evaluated.
Introduction
Garcinia genus belongs to the large family Clusiaceae (Guttiferae). A number of plants in this genus have been regarded as medicinal plants and they are used in folk medicine and food. Reports on Garcinia plants indicated that they produce a large number of biologically active substances such as flavonoids, polycyclic polyprenylated acylphloroglucinols (PPAPs), xanthones and terpenoids (Ciochina and Grossman, 2006, Hongthong et al., 2016, Reutrakul et al., 2007, Reutrakul et al., 2010), and some of which display remarkable biological activities.
Garcinia nuntasaenii Ngerns. & Suddee (Clusiaceae) was recently identified as a previously unclassified species in the Garcinia genus (Ngernsaengsaruay and Suddee, 2016). It is a shrub growing up to 1–2-m in height with white flowers and green fruits and commonly called “Chang-nga-ek” in Thai. It was sporadically found in the open-dry evergreen forest of the northeastern part of Thailand and its root is used in Thai folk medicine for treatment of muscle pain. Preliminary screening of the crude n-hexane, ethyl acetate and methanol extracts of the roots of G. nuntasaenii showed significant anti-inflammatory and anti-HIV activities. In the course of our continuing efforts to search for biologically active substances from plants in the Garcinia genus, we report the isolation and structural identification of previously undescribed compounds including three polycyclic polyprenylated acylphloroglucinols 1–3, three biphenyl derivatives 4–6, and a triterpene 7 (Fig. 1), along with thirteen known compounds 8–20 (Scheme S1) from the roots of G. nuntasaenii. The structures of these compounds were established via spectroscopic data or by comparison with the literature data. The biological activities of the isolated compounds were evaluated in a cytotoxicity assay against a panel of cultured mammalian cancer cell lines and in an anti-HIV-1 in vitro system. This work represents the first phytochemical investigation of the plant species.
Section snippets
Results and discussion
Garcinuntin A (1) was obtained as colorless needles and its molecular formula C38H50O4 was determined on the basis of the HRESIMS peak at m/z 593.3600 [M + Na]+ (calcd for C38H50O4Na, 593.3601). The major peaks at 1716, 1694 and 1640 cm−1 in its FT-IR spectrum indicated the presence of three carbonyl groups in the molecule. The UV spectrum showed the absorption bands at λmax 197, 247 and 277 nm in MeCN. The 1H NMR spectroscopic data (Table 1) revealed the presence of monosubstituted phenyl
Conclusion
Seven previously undescribed compounds, including polycyclic polyprenylated acylphloroglucinols (Type A PPAPs) 1–3, biphenyls 4–6, and a lanostane triterpene 7 were isolated from the roots of G. nuntasaenii along with thirteen known compounds (8–20). Of particular interest is the isolation of PPAPs (Type A) which are rarely found in the Garcinia genus. The structures and absolute configurations of compounds 1–3 were further confirmed by single X-ray crystallography and ECD calculations. Only
General experimental procedures
Melting points (uncorrected) were recorded in Celsius (°C) and measured on a digital Sanyo Gallenkamp. IR spectra were obtained on a Perkin Elmer EX FT-IR system spectrometer or a Bruker FT-IR spectrometer, model ALPHA; major bands (νmax) were recorded in wave number (cm−1). UV absorption spectra were performed on a JASCO V-530 spectrometer; principle bands (λmax) were recorded as wavelengths (nm) and log ε in methanol or acetonitrile. Optical rotations were measured on a JASCO DIP-370 digital
Notes
The authors declare no competing financial interest.
Acknowledgments
This work was supported by the Center of Excellence for Innovation in Chemistry (PERCH-CIC), the Office of the Higher Education Commission and Mahidol University under the National Research Universities (NRU), and International Laboratories Corp., Ltd. We thank Ms. Rungthip Kunthom at National Science and Technology Development Agency (NSTDA) for the collection of the crystallographic data of compounds 2 and 7.
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2020, Phytochemistry LettersCitation Excerpt :The key NOESY correlations of the β-orientation were H-8/H3-19, H-8/H3-18 and H3-18/H-20 (Fig. 3). The relative stereochemistry assigned for the lanostane core structure was established by NOESY experiments, a well-established biosynthetic pathway (Shibuya et al., 2004) as well as the previously reported works on the isolation of well-known lanostane-type triterpenes (Isaka et al., 2020; Chen et al., 2018; Chaturonrutsamee et al., 2018; Hongthong et al., 2016). Based on the spectroscopic data of 1 as described above and the comparison with the related derivatives, (E)-3β,9α-dihydroxylanosta-24-en-26-oic acid (Bui et al., 2016) and wallichinane B (6) (Hongthong et al., 2016), the structure of compound 1 was assigned as (22E,24E)-3β,9α-dihydroxylanosta-22,24-dien-26-oic acid and named as wallichinane F.
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2019, Bioorganic ChemistryCitation Excerpt :Among them, polyprenylated acylphloroglucinols feature a highly oxygenated bicyclo-[3.2.1]-octane-2,4,8-trione or bicyclo-[3.3.1]-nonane-2,4,9-trione core decorated with prenyl or geranyl side chains and show considerable structural diversity [6]. Further pharmacological investigations revealed that these kinds of metabolites exhibited broad biological activities, including antitumor [7,8], antibacterial [9], antioxidant [10], anti-HIV [11], antiangiogenic [12] and anti-inflammatory activities [13]. Due to their structural complexity and diversity and potential pharmacological effects, these kinds of metabolites have attracted broad scientific interest [14,15].
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2018, PhytochemistryCitation Excerpt :Clusiaceae plants are known to produce a battery of structurally diverse and bioactive benzophenones, especially polyprenylated benzophenones (PPBS) which can be classified into four types A–B (Wu et al., 2014) based up on the benzophenone skeletons and the substituent groups. Benzophenones exhibit a range of biological activities including anti-HIV (Pailee et al., 2018; Zhu et al., 2014), antimicrobial (Lokvam et al., 2000; Mahamodo et al., 2014), antioxidant (Ting et al., 2014), antiviral (Zhang et al., 2014), antiplasmodial (Marti et al., 2010), and cytotoxic (Chaturonrutsamee et al., 2018; Liu et al., 2013; Tian et al., 2016, 2017; Zhang et al., 2010). The properties of PPBS will be concerned strongly in the fields of natural products chemistry, synthetic chemistry (Boyce et al., 2016), pharmacology, food chemistry, and agricultural science (Wu et al., 2014).