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A novel γ-lactone derivative from the twigs of Turraea pubescens

  • Yao-Wen Chang , Chun-Mao Yuan , Jing Zhang , Yu Zhang , Hui-Ming Hua EMAIL logo , Ying-Tong Di EMAIL logo and Xiao-Jiang Hao
Published/Copyright: July 7, 2015
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Zeitschrift für Naturforschung B
From the journal Zeitschrift für Naturforschung B Volume 70 Issue 8

Abstract

A novel γ-lactone derivative, turranin G (1), and five known compounds were isolated from the twigs of Turraea pubescens. The structures of 1–6 were determined by means of spectroscopic analysis. The biogenetic pathway of compound 1 was proposed. Compound 2 exhibited inhibitory activity against lipopolysaccharide-induced nitric oxide in RAW264.7 cells with an IC50 value of 18.8 μm.

Keywords: anti-inflammatory activity; γ-lactone derivative; Turraea pubescens

1 Introduction

The genus Turraea (Meliaceae) including 60 species is distributed mainly in the tropical and subtropical areas of South and Southeast Asia and Western Australia [1]. To date, a series of limonoids, triterpenoids, and pregnanes with wide biological activities have been reported from this genus [2–4]. In China, there is only one species, Turraea pubescens Hellen, distributed in Hainan Province. The twigs and leaves of the title plant have been used in Chinese folklore medicine for the treatment of dysentery, pharyngolaryngitis, and traumatic hemorrhage [5]. As a part of our continuous search for potentially bioactive secondary metabolites from Meliaceae family [6–10], a new γ-lactone derivative, turranin G (1), along with five known compounds, dehydrodiconiferyl alcohol (2) [11, 12], turrapubesin F (3) [13], syringylglycerol (4) [14], sinapyl alcohol (5) [14, 15], and guaia-cylglycerol (6) [16], was isolated and identified from the twigs of the titled plant (Fig. 1). Compounds 1–3 were evaluated for cytotoxic and anti-inflammatory activities.

Fig. 1: Chemical structures of 1–6.
Fig. 1:

Chemical structures of 1–6.

2 Results and discussion

Turranin G (1) gave the molecular formula C22H38O6 from its molecular ion peak [M]+ at m/z = 398.2676 from the high-resolution electron impact mass spectroscopy (HR-EI-MS) requiring four degrees of unsaturation. The IR spectrum suggested the existence of γ-lactone moiety (1753 cm−1) and hydroxyl group (3423 cm−1). The 1H spectrum (see Supplementary Information available online) showed the presence of an O-methyl (δH = 3.36 ppm, s), a triplet methyl (δH = 0.87 ppm, t, J = 7.0 Hz), four olefinic protons (δH = 6.47 ppm, dd, J = 15.0, 10.6 Hz; 5.95 ppm, t, J = 10.6 Hz; 5.58 ppm, dd, J = 15.0, 10.6 Hz, and 5.38 ppm, dd, J = 10.6, 7.3 Hz), and four hydroxy protons (δH = 4.07 ppm, 4.04, 3.93, and 3.76). The 13C NMR spectrum (Supplementary Information available online) indicated the presence of 22 carbon signals, which were categorized by distortionless enhancement by polarization transfer experiments as two methyls (one methoxyl), one methylene, seven methines (four olefinic and two oxygenated), one ester carbonyl, and one ketal group. Apart from three degrees of unsaturation consumed by a carbonyl group and two double bonds, the remaining one suggested that compound 1 possesses one ring system.

The combined use of 1H–1H correlation spectroscopy, heteronuclear single-quantum coherence, and heteronuclear multiple-bond correlation (HMBC) (Supplementary Information available online) on 1 allowed us to establish one protonated partial structure from C-3 to C-21, in bold as shown in Fig. 2a. In the HMBC spectrum, cross peaks of H2-1, H-4, and OMe-2, to C-2 (δC = 110.0 ppm) showed that C-1, C-3, and OMe were connected to each other via C-2. Moreover, a γ-lactone ring was constructed by the key HMBC correlations of H-3, H-4, and H2-6 to ester carbonyl at C-5 (δC = 178.0 ppm). Thus, the gross structure of 1 was established as depicted.

Fig. 2: Selected 2D NMR correlations of compound 1.
Fig. 2:

Selected 2D NMR correlations of compound 1.

The relative configuration of 1 was mainly assigned by the rotating frame Overhauser effect spectroscopy (ROESY) experiment (Fig. 2b and Supplementary Information available online). The ROESY correlations of H-3/OMe and H-6a indicated that H-3, OMe, and the aliphatic chain located at the same side, and arbitrarily was defined as α-orientation. In the ROESY spectrum, cross peaks of H-12/H-13 and H-13/H-15 showed that H-12, H-13, and H-15 were located at the same side, while cross peaks of H2-11/H-14 and H-14/H-16 implied that H2-11, H-14, and H-16 were at the other side. Therefore, the geometry of the Δ12–13 and Δ14–15 double bond was determined as Z- and E-form, respectively.

Biogenetically, turranin G (1) might be originated from (3Z,13Z,15E)-17-hydroxy-2,5-dioxodocosa-3,13,15-trienoic acid (i) as shown in Scheme 1. i could convert to key intermediate ii via Claisen condensation and decarboxylation. Then, oxidative cleavage of the carbon–carbon double bond between C-3/C-4 in ii followed by the disproportionation reaction might produce iii. Finally, turranin G (1) could be formed via recyclization and methylation from iii.

Scheme 1: Proposed biogenetic pathway of compound 1.
Scheme 1:

Proposed biogenetic pathway of compound 1.

Compounds (1–3) were screened for their cytotoxic activities and anti-inflammatory activities against lipopolysaccharide (LPS)-induced nitric oxide (NO) production in RAW264.7 cells (Supplementary Information available online). Only compound 2 exhibited inhibitory activity against LPS-induced NO in RAW 264.7 cells with an IC50 value of 18.8 μm.

3 Experimental section

3.1 General experimental procedures

Optical rotations were determined on a JASCO P-1020 digital polarimeter (Jasco, Tokyo, Japan). UV spectra were detected on a Shimadzu UV-2401 PC spectrophotometer (Shimadzu, Tokyo, Japan). IR spectra were scanned with a Bruker Tensor-27 infrared spectrometer with a KBr disk (Bruker, Karlsruhe, Germany). Brucker HCT/E squire (Bruker, Karlsruhe, Germany) and Waters Autospec Premier P776 spectrum (Waters, Millford, MA, USA) were used to measure ESI-MS, EI-MS, and HR-EI-MS, respectively. 1D and 2D NMR spectra were recorded on Bruker AM-400 and DRX-500 spectrometers (Bruker, Karlsruhe, Germany) with trimethylsilyl as internal standard. Column chromatography was performed on silica gel (200–300 and 300–400 mesh; Qingdao Marine Chemical Inc., Qingdao, China), MCI gel CHP 20P (75–150 mm; Mitsubishi Chemical Corporation, Tokyo, Janpan), Sephadex LH-20 (40–70 mm; Amersham Pharmacia Biotech AB, Uppsala, Sweden), and Chromatorex RP-C18 gel (20–45 mm; Merck, Darmstadt, Germany). Thin layer chromatography (TLC plates; Qingdao Marine Chemical Inc., Qingdao, China) spots were visualized under UV light and by dipping into 5 % H2SO4 in EtOH followed by heating.

3.2 Plant material

The dried twigs of T. pubescens were collected in Dongfang, Hainan Province, China, in March 2012 and were identified by Prof. Yu Chen. A voucher specimen (H201203001) was deposited at the Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese Academy of Sciences.

3.3 Extraction and isolation

The air-dried powdered twigs of T. pubescens (12.0 kg) were extracted with MeOH. The combined MeOH extracts were concentrated under vacuum to give a crude residue, which was suspended in water and then partitioned successively with EtOAc. The EtOAc portion (200 g) was chromatographed on a silica gel column, eluted with petroleum ether–ethyl acetate (from 100:1 to 1:0) to yield six fractions (Fr. 1–6). Fr. 4 (46 g) was then separated on an MCI column (petroleum MeOH–H2O from 3:7 to 10:0) to obtain five fractions (4A–4E). Fr. 4C (5.6 g) was then chromatographed on a C18 column (petroleum MeOH–H2O 60:40, 65:45 and 70:30) to give three fractions (4C1–4C3). With further purified by the silica gel column and Sephadex LH-20 (MeOH), we obtain 1 (2 mg), 2 (11 mg), and 3 (5 mg) from Fr. 4C1 (100 mg), and 4 (3.5 mg), 5 (15 mg), and 6 (4 mg) from Fr. 4C2 (2.0 g).

3.4 Identification

Turranin G (1): Colorless solid. 1H NMR and 13C NMR data: see Table 1. – [α]D28 = −15.6 (c = 0.13, CH3OH). – IR (KBr): vm = 3423 (OH), 1753 (C=O), 1630, 1300, 1191, 1075, 1026, 708 cm−1. – UV (MeOH): λmax (lg εmax) = 231 nm (2.21). – MS ((+)-ESI): m/z = 399 [M + H]+. – HRMS (EI, 70 eV): m/z (%) = 398.2676 (100) (calcd. 398.2663 for C22H38O6+, [M]+).

Table 1

1H (400 MHz) and 13C (100 MHz) data of turranin G (1) in CDCl3.

No.δH (J, Hz)δCNo.δH (J, Hz)δC
13.93, d (12.2)

3.76, d (12.2)		60.0125.38, dt (10.6, 7.3)132.9
2110135.95, t (10.6)129.4
34.07, d (6.1)76.8146.47, dd (15.0, 10.6)126.5
42.63, m50.7155.58, dd (15.0, 6.6)137.3
5178.0164.04, dd (13.0, 6.3)73.4
6a1.62, m30.7171.47, m38.4
6b1.74, m
71.46, m28.0181.35, m26.3
81.33, m, 2H (overlapped)30.3191.28, m, 2H33.0
91.33, m, 2H (overlapped)30.0201.29, m, 2H23.7
101.39, m

1.47, m		30.6210.87, t (7.0), 3H14.4
112.17, m28.62-OCH33.36, s, 3H50.8

Attempts were made to determine the absolute configuration of C-16 of 1 by Mosher’s method. Due to the paucity of the sample (only 2 mg) these experiments proved to be unsuccessful, however.

4 Supplementary information

Data on the inhibition of nitric oxide production by compounds 1–3 and figures of the NMR spectra of turranin G (1) are given as Supplementary Information available online (doi:10.1515/znb-2014-0265).

Corresponding authors: Hui-Ming Hua, Key Laboratory of Structure-Based Drug Design and Discovery, Ministry of Education, Shenyang Pharmaceutical University, Shenyang 110016, Liaoning, P. R. China, Fax: +86-24-23986465, E-mail: ; and Ying-Tong Di, State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese Academy of Sciences, Kunming 650201, Yunnan, P. R. China, Fax: +86-871-65223070, E-mail:

Acknowledgments

This research was supported by the Young Academic and Technical Leader Raising Foundation of Yunnan Province (2009CI072) and the Chinese Academy of Sciences XiBuZhiGuang Project to Ying-Tong Di. We thank Prof. Y. Chen, Kunming Institute of Botany, Chinese Academy of Sciences (CAS), for the collection and identification of the plant material.

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Supplemental Material:

The online version of this article (DOI: 10.1515/znb-2014-0265) offers supplementary material, available to authorized users.

Received: 2014-11-25
Accepted: 2015-2-5
Published Online: 2015-7-7
Published in Print: 2015-8-1

©2015 by De Gruyter

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https://doi.org/10.1515/znb-2014-0265
Keywords for this article
anti-inflammatory activity; γ-lactone derivative; Turraea pubescens

Articles in the same Issue

  1. Frontmatter
  2. In this Issue
  3. Synthesis, crystal structure and magnetic characterization of a cyanide-bridged Mo–Ni nanosized molecular wheel
  4. A novel γ-lactone derivative from the twigs of Turraea pubescens
  5. A cyclic mixed-valence MoVI/MoV polyoxothiomolybdate cluster anion stabilized by a [(μ-I){Ag(PPh3)3}2]+ complex cation. Preparation and structure of [(μ-I){Ag(PPh3)3}2]2 [Mo8O8(μ-OH)2(μ-OEt)6(μ-S)8(μ3-O)4{Mo(DMF)2}] · 2EtOH
  6. Synthesis and characterization of silver(I) complexes of thioureas and thiocyanate: crystal structure of polymeric (1,3-diazinane-2-thione)thiocyanato silver(I)
  7. A molecular crown analogue templated by Keggin polyanions: synthesis, structure, and electrochemical and luminescent properties
  8. 1-(2′-Benzimidazolylmethyl)-pyridinium ylide in the one-pot synthesis of indolizine and benzimidazo[1,2-a]pyridine derivatives
  9. Orthoamide und Iminiumsalze, XC. Das RIBIL-Konzept – Reaktive Iminiumsalz-basierte ionische Flüssigkeiten
  10. Cyclophanes, Part 73: diastereoselective dimerization of an α,β-unsaturated ketone. Structure of all-trans-1,3-dibenzoyl-2,4-di([2.2]paracyclophan-4-yl)cyclobutane
  11. Crystal structures and luminescence properties of two Cd(II) complexes based on 2-(1H-imidazol-1-methyl)-6-methyl-1H-benzimidazole
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  13. Design and synthesis of quinazolinyl acetamides for their analgesic and anti-inflammatory activities
  14. Crystal structure and photoluminescence of a new two-dimensional Cd(II) coordination polymer based on 3-(carboxymethoxy)-2-naphthoic acid
  15. Synthesis, anti-HIV activity and molecular modeling study of 3-aryl-6-adamantylmethyl-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazole derivatives
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