Next Article in Journal
Synthesis and Antimicrobial Evaluation of Some New Oxadiazoles Derived from Phenylpropionohydrazides
Previous Article in Journal
Modeling the LPS Neutralization Activity of Anti-Endotoxins
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Molecules
Volume 14
Issue 5
10.3390/molecules14051889
molecules-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Sesquiterpenes from Laurencia similis

by
Hua Su
1, 2,
Da-Yong Shi
1,
Jing Li
1, 2,
Shu-Ju Guo
1, 2,
Li-Li Li
1, 2,
Zhao-Hui Yuan
1,* and
Xiao-Bin Zhu
1,*
1
Institute of Oceanology, Chinese Academy of Sciences, Qingdao 266071, China
2
Graduate School of the Chinese Academy of Sciences, Beijing 100049, China
*
Authors to whom correspondence should be addressed.
Molecules 2009, 14(5), 1889-1897; https://doi.org/10.3390/molecules14051889
Submission received: 17 March 2009 / Revised: 21 April 2009 / Accepted: 27 April 2009 / Published: 20 May 2009
Browse Figures
Versions Notes

Abstract

:
One new sesquiterpene, (4E)-1-bromo-5-[(1'S*,3'R*)-3'-bromo-2',2'-dimethyl-6'-methylenecyclohexyl]-3-methylpent-4-ene-2,3-diol (1), and fifteen known sesquiterpenes, isopalisol (2), luzonensol (3), palisadin B (4), aplysistatin (5), palisadin A (6), 4-hydroxyl-palisudin C (7), 5-acetoxypalisadin B (8), 10-hydroxyaristolan-9-one (9), aristol-8-en-1-one (10), aristolan-9-en-1-one (11), aristolan-1(10)-en-9-one (12), aristolan-1(10)-en-9-ol (13), aristolan-1(10),8-diene (14), aristolan-1,9-diene (15) and aristofone (16), were isolated from a sample of marine red alga Laurencia similis. Their structures were established by detailed NMR spectroscopic analysis and comparison with literature data. Compounds 2-9, and 16 were isolated for the first time from this species. All these metabolites were submitted for a cytotoxicity assay against the tumor cell line BEL7402 (human liver adenocarcinoma), but all of them were found inactive (IC50 > 10 μg/mL).

1. Introduction

Red algae of the genus Laurencia have proved to be a rich source of secondary metabolites, mainly sesquiterpenes, C15-acetogenins, and a few di- and triterpenes. More than 300 have been characterized from some 40 species collected in various parts of the world since the 1960s [1]. Many of these metabolites have been reported to possess a variety of biological activities, such as antimicrobial [2], antifeedant [3], anthelmintic [4,5], and cytotoxic activities [6,7].
Molecules 14 01889 g001 550
Figure 1. Structure of compounds 1 to 16.
Figure 1. Structure of compounds 1 to 16.
Molecules 14 01889 g001
Within the context of our program to systematically assess the chemical and biological diversity of marine algae distributed along the Chinese coast, further investigations of the chemical constituents of the red alga L. similis, collected from Sanya Bay, Hainan Province, led to the isolation and identification of one new sesquiterpene, which is described in this paper, together with 15 known sesquiterpenes.

2. Results and Discussion

The dried and powdered alga L. similis was extracted with 95% EtOH at room temperature. The concentrated extracts were partitioned between H2O and EtOAc. The EtOAc-soluble fraction was purified by a combination of silica gel and Sephadex LH-20 column chromatography, as well as preparative TLC procedures, to yield compounds 1-16.
Compound 1 was isolated as colorless oil, and showed IR absorptions for hydroxy functional group (3410 cm-1). The positive ESIMS exhibited a characteristic quasi-molecular ion peak cluster at m/z 399/401/403 (1:2:1) [M-H2O+Na]+, suggested the presence of two bromine atoms in the molecule. The molecular formula was deduced to be C15H24Br2O2 from the HRESIMS of the pseudomolecular ion ([M-H2O+Na]+, 401.1441), which indicated that there were three sites of unsaturation. 1H and 13C NMR data revealed the presence of two double bonds, both a terminal methylene [δH: 4.83 (s, 1H, H-7'α), 4.58 (d, 1H, J = 7.2 Hz, H-7'β); δC: 146.9 (C-6'), 110.3 (C-7')] and a 3,3-disubstituted propenyl [δH: 5.88 (dd, 1H, J =9.8, 15.5 Hz, H-5), 5.57(d, 1H, J =15.5 Hz, H-4); δC: 128.5 (C-5), 136.6 (C-4)], and no any other multiple bonds signals. Thus, it required 1 to be monocyclic. The NMR data (Table 1) demonstrated the presence of three methyls, three methylenes, three methines, and two quaternary carbons in addition to the four olefinic carbons. Comparison of the NMR data of 1 with the Compound 2 suggested that it had the same cyclohexane ring portion. This portion could be connected by HMBC data, including from H3-8' and H3-9' to C-1', C-2' and C-3', from H2-7' to C-1' and C-5'. The third spin system was also established by the HMBC data, including between H3-6 and C-2, C-3 and C-4, between H-4 and C-3 and C-1'. Furthermore, the connectivity of C-1' and C-5 was also established by the HMBC data from H-1' to C-4, C-5, C-2', C-6', C-7' and C-8'. Thus, the planar structure of 1 was clearly established.
Table
Table 1. 1H- and 13C-NMR Data of 1. NMR data were measured at 500 MHz for proton and at 125 MHz for carbon in CDCl3 for 1 (δ in ppm, J in Hz.). Assignments were corroborated by 1H, 1H-COSY, HMQC, and HMBC experiments.
Table 1. 1H- and 13C-NMR Data of 1. NMR data were measured at 500 MHz for proton and at 125 MHz for carbon in CDCl3 for 1 (δ in ppm, J in Hz.). Assignments were corroborated by 1H, 1H-COSY, HMQC, and HMBC experiments.
Pos.1
δHδCH→C (HMBC)
13.51(t, 11.2), 3.78(dd, 2.1, 11.2)46.7 (t)
23.69 (dd, J=2.1 Hz)77.6 (d)
374.2 (s)
45.57(d, 15.5)136.6 (d)C-3, C-1'
55.88 (dd, 9.8, 15.5)128.5 (d)
61.05 (s)24.3 (q)C-2, C-3, C-4
1'2.52 (d, 9.8)56.4 (d)C-4, C-5, C-2',C-6', C-7', C-8'
2'41.1 (s)
3'4.12 (dd, 4.2, 12.0)66.2 (d)
4'2.10 (m), 2.27 (m)36.4 (t)
5'2.10 (m), 2.37 (m)34.9 (t)
6'146.9 (s)
7'4.83 (s), 4.58 (d, 7.2)110.3 (t)C-1', C-5'
8'0.93 (s)16.2 (q)C-1', C-2', C-3', C-9'
9'1.34 (s)29.3 (q)C-1', C-2', C-3', C-8'
The relative configurations of 1 at C-1' and C-3' were shown to be the same as those of γ-ionone by analysis of a NOESY experiment and detailed NMR data comparison [8,9]. In the 2D NOESY spectrum, the observed correlations of H-1' with H-3' and Me-8' indicated the cis-orientation for these protons. The stereochemistry at C-3 and C-4 could not be determined unambiguously. The above spectral evidences established the structure for compound 1: (4E)-1-bromo-5-[(1'S*, 3'R*)-3'-bromo-2', 2'-dimethyl-6'-methylenecyclohexyl]-3-methylpent-4-ene-2, 3-diol.
Compounds 2-16 were identified as: isopalisol (2), luzonensol (3), palisadin B (4), aplysistatin (5), palisadin A (6), 4-hydroxyl-palisudin C (7), 5-acetoxypalisadin B (8), 10-hydroxyaristolan-9-one (9), aristol-8-en-1-one (10), aristolan-9-en-1-one (11), aristolan-1(10)-en-9-one (12), aristolan-1(10)-en-9-ol (13), aristolan-1(10),8-diene (14), aristolan-1,9-diene (15), aristofone (16),respectively, by spectroscopic analysis (1H-NMR, 13C-NMR, and MS) and comparisons with literature data [10,11,12,13,14,15,16,17]. Compounds 2-8 and 16 were isolated from this specimen for the first time.
Compounds 1–16 were evaluated for the cytotoxicity against a human liver adenocarcinoma (BEL7402) cell line. However, all of them were found to be inactive (IC50 >10 μg/mL).
Molecules 14 01889 g002 550
Figure 2. Selected HMBC and NOESY correlations of compound 1.
Figure 2. Selected HMBC and NOESY correlations of compound 1.
Molecules 14 01889 g002

3. Experimental

3.1. General

1D and 2D NMR spectra were obtained on a Bruker Avance500 spectrometer at 500 and 125 MHz for 1H and 13C, respectively. Mass spectra were collected using a VG Autospec 3000 mass spectrometer. Column chromatography (CC) was performed on silica gel (200–300 mesh, Qingdao Haiyang Chemical Co., Qingdao, China) and Sephadex LH-20 (Sigma). TLC was carried out with precoated silica gel plates (GF-254, Qingdao Haiyang Chemical Co., Qingdao, China).

3.2. Alga material

The marine red alga L. similis was collected from Hainan coastlines of People’s Republic of China, in May 2006 and identified by Prof. L.-P. Ding at the Institute of Oceanology, Chinese Academy of Sciences (IOCAS). A voucher specimen (No.2006037) was deposited in the Herbarium of Marine Organisms at IOCAS.

3.3. Extraction and Isolation

The air-dried alga L. similis (1.1 kg) was powdered and extracted with 95% EtOH at room temperature. The resulting extractive solution was filtered and evaporated under reduced pressure (<45 ℃) to yield a dark residue (34.2 g), and then partitioned between H2O and EtOAc. The EtOAc phase (28.5 g) was subjected to column chromatography (CC) over silica gel eluting with a gradient of increasing EtOAc in petroleum ether (PE, 0~100%) to give 7 fractions on the basis of TLC analysis. Fraction III (1.9 g) were further chromatographed over Sephadex LH-20 eluting with PE-CHCl3-MeOH (5:5:1) to yield compounds 1 (6.8 mg), 2 (5.7 mg), 4 (6.7 mg), 5 (7.3 mg) and 8 (7.3 mg) respectively. Fraction IV (0.6 g) was further chromatographed over Si gel eluting with a gradient of increasing EtOAc (35-100%) in PE to yield 3 (8.3 mg), 6 (7.9 mg), 10 (8.6 mg), 11 (10.0 mg), 14 (5.6 mg) and 16 (5.6 mg). Fraction Ⅴ (3.6 g) was decolored by column chromatography over Sephadex LH-20 eluting with PE-CHCl3-MeOH (5:5:1) and preparative TLC (PE/EtOAc 40:3) to afford compound 7 (7.3 mg), 9 (8.3 mg), 12 (11.1 mg), 13 (9.7 mg) and 15 (7.5 mg).
(4E)-1-bromo-5-[(1'S*, 3'R*)-3'-bromo-2', 2'-dimethyl-6'-methylenecyclohexyl]-3-methylpent-4-ene-2, 3-diol (1): colorless oil; IR (film) vmax 3410, 3012, 2921, 1440, 1065, 990 cm-1; [α]20D +18.4 (CHCl3, c 0.30); 1H NMR (CDCl3) (see Table 1); 13C NMR data (CDCl3) (see Table 1). ESI-MS: m/z 399/401/403 (1:2:1) [M-H2O+Na]+. HR-ESI-MS: m/z 401.1441([M-H2O+Na]+) (calcd for 401.1426, C15H22Br2ONa).
Isopalisol (2): C15H23BrO, colorless oil; EI-MS m/z(%): 282 (3), 280 (3, M-H2O), 265 (8), 201 (15), 121 (100), 105 (48), 93 (55); 1H-NMR(CDCl3, 500MHz) δ: 3.45 (2H, m, H2-1), 4.22 (1H, t, J=5.0Hz, H-2), 5.48 (1H, m, H-4), 2.25 (1H, m, H-5α), 2.90 (1H, m, H-5β), 2.00 (1H, m, H-6), 2.64 (2H, m, H2-8), 5.52 (1H, m, H-9), 5.37 (1H, m, H-10), 0.95 (3H, s, H3-12), 1.02 (3H, s, H3-13), 4.60 (1H, s, H-14α), 4.86 (1H, s, H-14β),1.65 (3H, s, H3-15); 13C-NMR(CDCl3, 125MHz) δ: 38.5 (t, C-1), 76.5 (d, C-2), 133.4 (s, C-3), 128.4 (d, C-4), 25.2 (t, C-5), 52.4 (d, C-6), 145.5 (s, C-7), 32.4 (t, C-8), 123.1 (d, C-9), 136.9 (q, C-10), 37.1 (s, C-11), 25.1 (q, C-12), 30.3 (q, C-13), 109.7 (t, C-14), 12.2 (q, C-15).
Luzonensol (3): C15H24Br2O, colorless oil; EI-MS m/z: 364 (3), 362 (6), 360 (3, M-H2O), 281 (100), 201 (47),147 (30), 121 (80); 1H-NMR(CDCl3, 500MHz) δ: 3.49 (1H, dd, J=9.0, 10.0 Hz, H-1α), 3.40 (1H, dd, J=4.5, 10.0 Hz, H-1β), 4.74 (1H, dd, J=4.5, 9.0 Hz, H-2), 5.29 (1H, m, H-4), 2.45 (1H, m, H-5α), 2.25 (1H, m, H-5β), 1.83 (1H, m, H-6), 2.04 (1H, m, H-8α), 2.35 (1H, m, H-8β), 2.08 (1H, m, H-9α), 2.30 (1H, m, H-9β), 4.15 (1H, dd, J=4.5, 11.5Hz, H-10), 0.87 (3H, s, H3-12), 1.20 (3H, s, H3-13), 4.56 (1H, s, H-14α), 4.91 (1H, s, H-14β), 1.69 (3H, s, H3-15); 13C-NMR(CDCl3,125MHz) δ: 36.9 (t, C-1), 70.1 (d, C-2), 133.1 (s, C-3), 129.9 (d, C-4), 24.7 (t, C-5), 53.2 (d, C-6), 145.3 (s, C-7), 37.2 (t, C-8), 35.6 (t, C-9), 66.7 (d, C-10), 41.6 (s, C-11), 16.6 (q, C-12), 28.4 (q, C-13), 110.0 (t, C-14), 17.4 (q, C-15).
Palisadin B (4): C15H24OBr2, colorless oil; ESI-MS m/z: 378/380/382; 1H-NMR (CDCl3, 500MHz) δ: 3.41 (1H, dd, J=7, 11Hz, H-1α), 3.73 (1H, dd, J=3, 11Hz, H-1β), 4.54 (1H, m, H-2), 5.63 (1H, d, J=8 Hz, H-4), 2.05 (3H, m, H2-5 and H-6), 1.77 (2H, m, H2-8), 2.25 (2H, m, H2-9), 3.95 (1H, dd, J=5, 12 Hz, H-10), 1.27 (3H, s, H3-12), 1.36 (3H, s, H3-13), 0.95 (3H, s, H3-14), 1.15 (3H, s, H3-15); 13C-NMR(CDCl3,125MHz) δ: 36.2 (t, C-1), 70.7 (d, C-2), 136.1 (s, C-3), 129.4 (d, C-4), 25.9 (t, C-5), 52.8 (d, C-6), 77.5 (s, C-7), 36.7 (t, C-8), 32.9 (t, C-9), 66.3 (d, C-10), 40.8 (s, C-11), 21.0 (q, C-12), 22.0 (q, C-13), 17.9 (q, C-14), 30.7 (q, C-15).
Aplysistatin (5): C15H21BrO3, colorless oil; EI-MS m/z: 330/328[M]+ (1), 300/298 (4), 286/284(8), 249(5), 218/216(8), 204/202(33), 189/187(19), 139(24), 123(100), 107(39); 1H-NMR (CDCl3, 500MHz) δ: 0.96(3H, s, H3-13), 1.18(3H, s, H3-15), 1.30(3H, s, H3-14), 3.86(1H, dd, J = 7.0 , 9.0 Hz, H-1α), 3.91(1H, m, H-10), 4.48(1H, t, J = 9.0, 9.0 Hz, H-1β), 5.13(1H, m, H-2), 6.95(1H, m, H-4). 13C-NMR (CDCl3,125MHz) δ: 69.9(C-1), 66.8(C-2), 132.0(C-3), 143.0(C-4),27.2(C-5), 51.3(C-6), 79.0(C-7), 32.4(C-8), 37.7(C-9), 65.1(C-10), 41.0(C-11), 169.3(C-12), 18.0(C-13), 30.7(C-14), 21.7(C-15).
Palisadin A (6): C15H23BrO2, colorless oil; EI-MS m/z: 314/316; 1H-NMR (CDCl3, 500MHz) δ: 1.00(3H, s, H3-14), 1.25(3H, s, H3-15), 1.37(3H, s, H3-13), 1.55(1H, m, H-8α), 1.85(1H, m, H-8β), 2.25(2H, m, H2-9), 2.40(2H, m, H2-5), 2.40(1H, m, H-6), 3.93(1H, dd, J = 8.0, 8.0 Hz, H-1α), 3.95(1H, dd, J = 5.0, 12.0 Hz, H-10), 4.10(1H, dd, J = 8.0, 8.0 Hz, H-1β), 4.45(2H, m, H2-12), 4.83(1H, m, H-2), 5.63(1H, br s, H-4). 13C-NMR (CDCl3, 125MHz) δ: 75.4(C-1), 71.0(C-2), 141.9(C-3), 121.1(C-4), 26.3(C-5), 51.8(C-6), 78.0(C-7), 37.6(C-8), 32.7(C-9), 66.2(C-10), 41.0(C-11), 72.0(C-12), 21.9(C-13), 18.0(C-14), 30.8(C-15).
4-hydroxyl-Palisudin C (7): C15H24Br2O2, colorless oil; EIMS: m/z 394 396 398 [M]+ (1:2:1), 376 378 380 [M-H2O]+ (1:2:1); 1H-NMR (CDCl3, 500MHz) δ: 3.31 (1H, t, J = 10.5 Hz, H-1α), 3.44 (1H, dd, J = 8.8, 10.5 Hz, H-1β), 4.43 (1H, d, J = 7.7 Hz, H-2), 4.86 (1H, t, J = 8.1 Hz, H-4), 1.43–1.46 (1H, m, H-5α), 2.20–2.24 (1H, m, H-5β), 1.61–1.62 (1H, m, H-6), 1.59–1.60 (1H, m, H-8α), 1.70–1.73 (1H, m, H-8β), 2.05–2.07 (1H, m, H-9α), 2.22–2.23 (1H, m, H-9β), 3.90 (1H, dd, J = 4.3,12.8 Hz, H-10), 4.91 (1H, s, H-12α), 5.23 (1H, s, H-12β), 1.26 (3H, s, H3-13), 0.97 (3H, s, H3-14), 1.10 (3H, s, H3-15); 13C-NMR (CDCl3, 125MHz) δ: 37.3 (t, C-1), 70.9 (d, C-2), 153.2 (s, C-3), 68.8 (d, C-4), 34.9 (t, C-5), 48.8 (d, C-6), 77.5 (s, C-7), 36.9 (t, C-8), 32.3 (t, C-9), 66.1 (d, C-10), 40.3 (s, C-11), 107.1 (t, C-12), 22.3 (q, C-13), 17.8 (q, C-14), 30.8 (q, C-15).
5-Acetoxypalisadin B (8): C17H26Br2O3, colorless oil; EI-MS m/z(%): 436/438/440; 1H-NMR (CDCl3, 500MHz) δ: 1.01(3H, s, H3-14), 1.20(3H, s, H3-15), 1.63(3H, s, H3-13), 1.80(3H, s, H3-12), 2.08(3H, s, H3-OAc), 1.58(1H, m, H-8α), 1.84 (1H, m, H-8β), 1.73(1H, m, H-6), 2.15~2.31(2H, m, H2-9), 3.41(1H, dd, J = 8.0, 11.0 Hz, H-1α), 3.70(1H, dd, J = 3.0, 11.0 Hz, H-1β), 3.87(1H, dd, J = 4.0, 12.0 Hz, H-10), 4.44(1H, d, J = 10.0 Hz, H-2), 5.69(1H, d, J = 8.0 Hz H-4), 5.78(1H, d, J = 8.0 Hz, H-5); 13C-NMR(CDCl3,125MHz) δ: [25.2, 170.3(C-OAc)], 34.8(C-1), 70.1(C-2), 142.5(C-3), 127.0(C-4), 69.6(C-5), 53.7(C-6), 77.8(C-7), 39.3(C-8), 32.7(C-9), 66.1(C-10), 41.3(C-11), 21.2(C-12), 21.5(C-13), 18.7(C-14), 30.8(C-15).
10-Hydroxyaristolan-9-one (9): C15H24O2, colorless oil; FAB-MS(pos.): 236 [M]+; 1H-NMR (CDCl3, 500MHz) δ: 0.80(1H, d, J = 9.1 Hz, H-6), 0.94(3H, d, J = 6.7 Hz, H3-14), 1.05(3H, s, H3-12), 1.06(3H, s, H3-13), 1.20(3H, s, H3-15), 1.22~1.33(3H, m, H2-3 and H-7), 1.38(1H, m, H-1α), 1.47 (1H, m, H-4), 1.56 (1H, m, H-2α), 1.65 (1H, m, H-2β), 1.92(1H, m, H-1β), 2.26 (1H, d, J=17.0 Hz, H-8α), 3.09 (1H, dd, J = 9.0, 17.0 Hz, H-8β); 13C-NMR (CDCl3,125MHz) δ: 29.5 (t, C-1), 22.8 (t, C-2), 29.1 (t, C-3), 34.8 (d, C-4), 46.8 (s, C-5), 29.0 (d, C-6),22.9 (d, C-7), 34.5 (t, C-8),215.9 (s, C-9), 77.7(s, C-10), 21.0 (t, C-11), 16.8 (q, C-12), 30.6 (q, C-13),17.0 (q, C-14), 18.4 (q, C-15).
Aristol-8-en-1-one (10): C15H22O, colorless oil; FAB-MS (pos.): 218 [M]+; 1H-NMR (CDCl3, 500MHz) δ: 0.56 (3H, s, H3-15), 0.78 (1H, d, J = 8.5 Hz, H-6), 1.01 (3H, s, H3-12), 1.05 (3H, d, J = 6.6 Hz, H3-14), 1.16 (3H, s, H3-13), 1.23 (1H, dd, J = 5.6, 8.5 Hz, H-7), 1.69 (1H, m, H-3α), 1.94 (1H, m, H-3β), 1.96 (1H, m, H-4), 2.36 (2H, m, H2-2), 2.58 (1H, br s, H-10), 5.86 (1H, dd, J = 1.9, 10.1 Hz, H-9), 6.02 (1H, m, H-8, H-8). 13C-NMR (CDCl3, 125MHz) δ: 209.9 (s, C-1),40.5 (t, C-2), 31.4 (t, C-3), 40.1 (d, C-4),39.1 (s, C-5), 35.1 (d, C-6), 24.7 (d, C-7), 127.3 (d, C-8), 118.8 (d, C-9), 54.7 (d, C-10), 26.1 (s, C-11), 16.0 (q, C-12),30.5 (q, C-13), 15.5 (q, C-14), 15.9 (q, C-15).
Aristolan-9-en-1-one (11): C15H22O, colorless oil; 1H-NMR (CDCl3, 500MHz) δ: 0.71 (1H, d, J = 9.4 Hz, H-6), 0.87 (1H, m, H-7), 0.99 (3H, H, s, H3-15), 1.03 (3H, s, H3-12), 1.06 (3H, d, J = 6.8 Hz, H3-14), 1.07 (3H, s, H3-13), 1.73 (2H, m, H2-3), 1.98 (1H, m, H-4), 2.28 (1H, m, H-2α), 2.34 (1H, m, H-8α), 2.50 (1H, m, H-2β), 2.55 (1H, m, H- 8β), 6.41 (1H, m, H-9α). 13C-NMR (CDCl3, 125MHz) δ: 202.0 (s, C-1), 40.0 (t, C-2), 27.8 (t, C-3), 35.9 (d, C-4), 37.8 (s, C-5), 32.0 (d, C-6), 19.3 (d, C-7), 22.5 (t, C-8), 132.5 (d, C-9), 143.5 (s, C-10), 18.8 (s, C-11), 15.3 (q, C-12), 29.8 (q, C-13),15.4 (q, C-14), 22.6 (q, C-15).
Aristolan-1(10)-en-9-one (12): C15H22O, colorless oil; 1H-NMR (CDCl3, 500MHz) δ: 0.90 (1H, d, J = 9.4 Hz, H-6), 0.96 (1H, m, H-7), 0.99 (3H, s, H3-12), 1.02(3H, s, H3-15), 1.04 (3H, d, J = 5.8 Hz, H3-14), 1.05 (3H, s, H3-13), 1.50 (2H, m, H2-3), 1.76 (1H, m, H-4), 2.24 (2H, m, H2-2), 2.66 (1H, dd, J = 1.1, 20.0Hz, H-8α), 2.78 (1H, dd, J = 6.1, 20.0 Hz, H-8β), 6.71 (1H, m, H-1). 13C-NMR (CDCl3, 125MHz) δ: 136.4 (d, C-1), 25.9 (t, C-2), 26.1 (t, C-3), 36.7 (d, C-4), 37.6 (s, C-5),29.8 (d, C-6), 19.0 (d, C-7), 34.6 (t, C-8), 200.2 (s, C-9), 142.5 (s, C-10),18.7 (s, C-11), 14.8 (q, C-12), 30.1 (q, C-13),15.9 (q, C-14), 24.0 (q, C-15).
Aristolan-1(10)-en-9-ol (13): C15H24O, colorless needles ; 1H-NMR (CDCl3, 500MHz) δ: 0.53 (1H, d, J = 9.1 Hz, H-6), 0.75 (1H, m, H-7), 0.97 (3H, s, H3-12), 1.07(3H, s, H3-15), 0.95 (3H, d, J = 6.9 Hz, H3-14), 0.98 (3H, s, H3-13), 1.38 (2H, m, H2-3), 1.75 (1H, m, H-4), 2.01 (2H, m, H2-2), 1.22 (1H, m, H-8α), 2.32 (1H, m, H-8β), 5.53 (1H, m, H-1). 13C-NMR (CDCl3, 125MHz) δ: 116.4 (d, C-1), 25.4 (t, C-2), 26.7 (t, C-3), 36.9 (d, C-4), 38.8 (s, C-5), 32.9 (d, C-6),18.4 (d, C-7), 30.7 (t, C-8), 67.4 (d, C-9), 145.7 (s, C-10), 18.6 (s, C-11), 16.1 (q, C-12), 29.8 (q, C-13),16.6 (q, C-14),23.9 (q, C-15).
Aristolan-1(10)-8-diene (14): C15H22, colorless needles; 1H-NMR (CDCl3, 500MHz) δ: 0.94 (1H, d, J = 8.4 Hz, H-6), 1.17 (1H, dd, J = 5.3, 8.3 Hz, H-7), 0.92 (3H, s, H3-12), 0.96(3H, s, H3-15), 0.99 (3H, d, J = 6.9 Hz, H3-14), 1.11 (3H, s, H3-13), 1.53 (1H, m, H-3α), 1.67 (2H, m, H-3β and H-4), 2.16 (2H, m, H2-2), 5.73 (1H, dd, J = 5.3, 9.7 Hz,, H-8), 5.28 (1H, m, H-1), 5.85 (1H, d, J = 9.7Hz, , H-9). 13C-NMR (CDCl3, 125MHz) δ: 122.0 (d, C-1), 25.2 (t, C-2), 27.7 (t, C-3), 35.8(d, C-4), 34.6 (s, C-5), 34.5 (d, C-6), 24.4 (d, C-7), 124.3 (d, C-8), 126.7 (d, C-9), 141.7 (s, C-10), 26.3(s, C-11), 14.7(q, C-12), 29.3 (q, C-13), 15.9 (q, C-14), 23.0 (q, C-15).
Aristolan-1,9-diene (15): C15H22, colorless needles; 1H-NMR (CDCl3, 500MHz) δ: 0.67 (1H, d, J = 9.3 Hz, H-6), 0.81 (1H, dd, J = 7.1, 9.3 Hz, H-7), 1.03 (3H, m, H3-12), 0.96(3H, s, H3-15), 0.99 (3H, d, J = 6.9 Hz, H3-14), 1.04 (3H, m, H3-13), 1.90 (1H, dd, J = 11.2, 18.3 Hz, H-3α), 2.01(1H, m, H-3β), 5.55 (1H, dd, J = 5.6,9.8Hz, H-2), 2.23(1H, dd, J = 5.3, 20.1 Hz,, H-8α), 2.55(1H, dd, J = 7.1, 20.1 Hz, H-8β), 5.88 (1H, d, J = 9.8 Hz, H-1), 5.26 (1H, m, H-9). 13C-NMR (CDCl3, 125MHz) δ: 129.1(d, C-1), 125.2 (d, C-2), 32.3 (t, C-3), 34.1(d, C-4), 35.1 (s, C-5), 31.4 (d, C-6),19.7 (d, C-7), 22.4 (t, C-8), 122.7 (d, C-9),140.7 (s, C-10), 18.3(s, C-11),15.0(q, C-12), 29.9 (q, C-13),15.1 (q, C-14), 21.1 (q, C-15).
Aristofone (16): C15H22O, colorless needles; 1H-NMR (CDCl3, 500MHz) δ: 1.29~1.36 (3H, m, H2-1 and H-3β), 1.48 (1H, m, H-2β), 1.74~.178 (2H, m, H-2α and H-3α), 1.65 (1H, d, J = 8.0Hz, H-4), 2.18 (1H, d, J = 8.0 Hz, H-6), 2.34~2.40 (1H, m, H-7), 5.64 (1H, s, H-9), 1.40 (3H, s, H3-12), 1.92 (3H, s, H3-13), 0.99 (3H, dd, J = 2.4, 6.8 Hz, H3-14), 1.12 (3H, s, H3-15). 13C-NMR (CDCl3,125MHz) δ: 33.0 (t, C-l), 30.4 (t, C-2), 26.0 (t, C-3), 38.5 (d, C-4), 39.4 (s, C-5), 39.0(d, C-6), 35.4 (d, C-7), 195.9(s, C-8), 124.1 (d, C-9), 167.3 (s, C-l0), 24.1 (s, C-11), 16.2 (q, C-12), 29.5 (q, C-13), 22.4 (q, C-14), 16.3 (q, C-15); EIMS: 218 [M]+.

3.4. Cytotoxicity Assay

Cytotoxic assay toward the human liver adenocarcinoma (BEL7402) cell line was carried out as previously reported [18].

Acknowledgements

This work was financial supported by NSFC (No. 30530080), key Innovative Project of the Academy (No. KZCX2-YW-209), national 863 project (No. 2006AA06Z362, No. 2007AA09Z410, 2007AA091604) and National Science & Technology Pillar Program (No: 2006BAB03A12).
  • Samples Availability: Samples of the compounds are available from the authors.

References and Notes

  1. Erickson, K.L. In Marine Natural Products, Chemical and Biological Perspectives; Scheuer, P.J., Ed.; Academic Press: New York, USA, 1983; Volume V, pp. 131–257. [Google Scholar]
  2. Koenig, G.M.; Wright, A.D. Laurencia rigida: Chemical Investigations of Its Antifouling Dichloromethane Extract. J. Nat. Prod. 1997, 60, 967–970. [Google Scholar] [CrossRef]
  3. Kurata, K.; Taniguchi, K.; Agatsuma, Y.; Suzuki, M. Diterpenoid feeding-deterrents from Laurencia saitoi. Phytochemistry 1998, 47, 363–369. [Google Scholar] [CrossRef]
  4. Davyt, D.; Fernandez, R.; Suescun, L.; Mombr, A.W.; Saldaa, J.; Domnguez, L.; Coll, J.; Fujii, M.T.; Manta, E. New Sesquiterpene Derivatives from the Red Alga Laurencia scoparia. Isolation, Structure Determination, and Anthelmintic Activity. J. Nat. Prod. 2001, 64, 1552–1555. [Google Scholar] [CrossRef]
  5. Topcu, G.; Aydogmus, Z.; Imre, S.; Gören, A.C.; Pezzuto, J.M.; Clement, J.A.; Kingston, D.G. Brominated Sesquiterpenes from the Red Alga Laurencia obtusa. J. Nat. Prod. 2003, 66, 1505–1508. [Google Scholar] [CrossRef]
  6. Juagdan, E.G.; Kalidindi, R.; Scheuer, P. Two new chamigranes from an hawaiian red alga, Laurencia cartilaginea. Tetrahedron 1997, 53, 521–528. [Google Scholar] [CrossRef]
  7. Sun, J.; Shi, D.Y.; Ma, M.; Yang, Y.C.; Fan, X.; Shi, J.G. Sesquiterpenes from the Red Alga Laurencia tristicha. J. Nat. Prod. 2005, 68, 915–919. [Google Scholar] [CrossRef]
  8. Serra, S.; Fuganti, C.; Brenna, E. Synthesis, Olfactory Evaluation, and Determination of the Absolute Configuration of the 3,4-Didehydroionone Stereoisomers. Helv. Chim. Acta 2006, 89, 1110–1122. [Google Scholar] [CrossRef]
  9. Yuan, Z.-H.; Han, L.-J.; Fan, X.; Shi, J.-G. Two new norisoprenoid derivatives from the red alga Gymnogongrus flabelliformis. Chin. Chem. Lett. 2006, 17, 1205–1208. [Google Scholar]
  10. Masayuki, K.; Mong, S.M.; Tatsuo, H.; Ge´rald, B.; Charles, W.J. New Bromoterpenes from the Red Alga Laurencia luzonensis. J. Nat. Prod. 2001, 64, 696–700. [Google Scholar] [CrossRef]
  11. Paul, V.J.; Fenical, W. Palisadins A, B and related monocyclofarnesol-derived sesquiterpenoids from the red marine alga Laurencia cf. palisada. Tetrahedron Lett. 1980, 21, 2787–2790. [Google Scholar] [CrossRef]
  12. Pettit, G.R.; Herald, C.L.; Allen, M.S.; VonDreele, R.B.; Vanell, L.D.; Kao, J.P.Y.; Blake, W. Antineoplastic agents. 48. The isolation and structure of aplysistatin. J. Am.Chem. Soc. 1977, 99, 262–263. [Google Scholar]
  13. Ruecker, G.; Kretzuschmar, U. 9-Aristolen-la-01 und 1.2.9.1O-Tetradehydro-aristolan, neue Sesquiterpene mit einem Aristolan-Geruest. Liebigs Ann. Chem. 1971, 748, 214–217. [Google Scholar] [CrossRef]
  14. Takeshita, H.; Shimooda, I.; Hatsui, T. Synthetic Photochemistry. XXL. The Sensitized Photooxygenation of Calarene. A Facile Hock Cleavage of an Allylhydroperoxide and Structure Revision for Aristolenols. Bull. Chem. Soc. Jpn. 1980, 53, 3721–3722. [Google Scholar] [CrossRef]
  15. Ji, N.Y.; Li, X.M.; Ding, L.P.; Wang, B.G. Aristolane Sesquiterpenes and Highly Brominated Indoles from the Marine Red Alga Laurencia similis (Rhodomelaceae). Helv. Chim. Acta 2007, 90, 385–391. [Google Scholar] [CrossRef]
  16. Shide, L.; Olbrich, A.; Mayer, R.; Rccker, G. Gansongon, a New Aristolane Ketone from Nardostachys chinesis Batalin and structure revision of an Aristolenol. Planta Med. 1987, 53, 556–558. [Google Scholar] [CrossRef]
  17. Vidari, G.; Che, Z.; Garlaschelli, L. New nardosinane and aristolane sesquiterpenes from the fruiting bodies of Russula lepida. Tetrahedron Lett. 1998, 39, 6073–6076. [Google Scholar] [CrossRef]
  18. Berengeron, R.I.; Davanaugh, P.F., Jr.; Kline, S.J.; Hughes, R.G., Jr.; Elliot, G.T.; Porter, C.W. Antineoplastic and antiherpetic activity of spermidine catecholamide iron chelators. Bioche. Biophys. Res. Commun. 1984, 121, 848–854. [Google Scholar] [CrossRef]

Share and Cite

MDPI and ACS Style

Su, H.; Shi, D.-Y.; Li, J.; Guo, S.-J.; Li, L.-L.; Yuan, Z.-H.; Zhu, X.-B. Sesquiterpenes from Laurencia similis. Molecules 2009, 14, 1889-1897. https://doi.org/10.3390/molecules14051889

AMA Style

Su H, Shi D-Y, Li J, Guo S-J, Li L-L, Yuan Z-H, Zhu X-B. Sesquiterpenes from Laurencia similis. Molecules. 2009; 14(5):1889-1897. https://doi.org/10.3390/molecules14051889

Chicago/Turabian Style

Su, Hua, Da-Yong Shi, Jing Li, Shu-Ju Guo, Li-Li Li, Zhao-Hui Yuan, and Xiao-Bin Zhu. 2009. "Sesquiterpenes from Laurencia similis" Molecules 14, no. 5: 1889-1897. https://doi.org/10.3390/molecules14051889

APA Style

Su, H., Shi, D. -Y., Li, J., Guo, S. -J., Li, L. -L., Yuan, Z. -H., & Zhu, X. -B. (2009). Sesquiterpenes from Laurencia similis. Molecules, 14(5), 1889-1897. https://doi.org/10.3390/molecules14051889

Article Metrics

Back to TopTop