Tyrosine kinase inhibitors from the rainforest tree Polyscias murrayi

A series of 3-(4-hydroxyphenyl) propanoic acid derivatives, which inhibit Itk (interleukin-2 inducible T-cell kinase), a Th2-cell target, were isolated from the Australian rainforest tree Polyscias murrayi. The new compound 3-(4-hydroxyphenyl) propionyl choline and a 2:1 mixture of the new compounds 3,4-di-O-3-(4-hydroxyphenyl) propionyl-1,5-dihydroxycyclohexanecarboxylic acid and 3,5-di-O-3-(4-hydroxyphenyl) propionyl-1,4-dihydroxycyclohexanecarboxylic acid were isolated along with two known compounds 3-(4-hydroxyphenyl) propanoic acid and 3-(3,4-hydroxyphenyl) propanoic acid. Their structures were determined by 1D and 2D NMR spectroscopy. The assay results suggest that both the 3-(4-hydroxyphenyl) propanoate and carboxyl moieties contribute to Itk activity of the compounds.     

架棚中酚类化合物的研究

从架棚（ＣｅｒａｔｏｓｔｉｇｍａｍｉｎｕｓＳｔａｐｆｅｘＰｒａｉｎ）的乙酸乙酯部分分离得到１４个酚类化合物。经波谱技术,特别是２ＤＮＭＲ技术鉴定,其中化合物ｐｌｕｍｂｏｃａｔｅｃｈｉｎｓＡ（１）和Ｂ（２）为新化合物。其他１２个化合物被分别鉴定为ｐｌｕｍｂｏｌａｃｔｏｎｅＡ（３）、ｐｌｕｍｂａｂｉｃａｃｉｄ（４）、ｉｓｏｓｈｉｎａｎｏｌｏｎｅ（５）、ｅｐｉｓｏｓｈｉｎａｎｏｌｏｎｅ（６）、Ｎｔｒａｎｓｃａｆｅｏｙｌｔｙｒａｍｉｎｅ、Ｎｔｒａｎｓｆｅｒｕｌｏｙｌｔｙｒａｍｉｎｅ、ａｐｏｃｙｎｉｎ、ｖａｎｉｌｉｃａｃｉｄ、ｓｙｒｉｎｇｉｃａｃｉｄ、ｇａｌｏｃａｔｅｃｈｉｎ、（＋）ｃａｔｅｃｈｉｎ和１,２,６ｔｒｉＯｇａｌｏｙｌｇｌｕｃｏｓｅ。     

Azaphilones and Meroterpenoids from the Soft Coral-Derived Fungus Penicillium glabrum glmu003

Two new azaphilone compounds, daldinins G ( 1 ) and H ( 2 ), together with nine known compounds daldinin D ( 3 ), sargassopenilline B ( 4 ), austalide V ( 5 ), austalide K ( 6 ), austalide P ( 7 ), austalide P acid ( 8 ), austalide H ( 9 ), 13-O-deacetyaustalide I ( 10 ), and 17-O-demethylaustalide B ( 11 ), were isolated from the soft coral-derived fungus Penicillium glabrum glmu003. The new structures of 1 and 2 were elucidated on the basis of 1D and 2D NMR, mass spectra, and electronic circular dichroism (ECD) data analysis. Compound 5 showed weak inhibitory activity against pancreatic lipase (PL) with IC₅₀ value of 23.9 μg/mL.     

A new triterpene saponin from Chenopodium ficifolium

The new triterpene saponin 3-O-beta-D-glucopyranoside, 28-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosiduronic acid oleanolate was isolated from the roots of Chenopodium ficifolium. The known compounds stigmasterol-3-O-glucoside and 3-O-beta-D-glucopyranosiduronic acid, 28-beta-D-glucopyranosyl oleanolate were also isolated. The latter compound, oleanolic acid, beta-sitosterol and its glucoside were isolated from the aerial parts. The identity of these compounds was verified through different chemical and physico-chemical evidences including different 1D and 2D NMR experiments.     

Natural bromophenols from the marine red alga Polysiphonia urceolata (Rhodomelaceae): structural elucidation and DPPH radical-scavenging activity

Three new natural occurring bromophenols, 3-(3-bromo-4,5-dihydroxyphenyl)-2-(3,5-dibromo-4-hydroxyphenyl)propionic acid (1), (E)-4-(3-bromo-4,5-dihydroxyphenyl)-but-3-en-2-one (2), and (3,5-dibromo-4-hydroxyphenyl) acetic acid butyl ester (3), together with one known bromophenol, 1,2-bis(3-bromo-4,5-dihydroxyphenyl)ethane (4), were isolated and identified from the marine red alga Polysiphonia urceolata. The structures of these compounds were elucidated by extensive analysis of 1D and 2D NMR and IR spectra and MS data. Each of the isolated compounds was evaluated for scavenging alpha, alpha-diphenyl-beta-picrylhydrazyl (DPPH) radical activity and all of them exhibited significant activity with IC(50) values ranging from 9.67 to 21.90 microM, compared to the positive control, a well-known antioxidant butylated hydroxytoluene (BHT), with IC(50) 83.84 microM.     

Terpenoid and phenolic metabolites from the fungus xylaria sp. associated with termite nests

Three new sesquiterpene acids, xylaric acids A-C (1-3, resp.), and a new tetralone (=3,4-dihydronaphthalen-1(2H)-one) derivative, 4, along with nine known compounds, xylaric acid D (5), hydroheptelidic acid (6), gliocladic acid (7), chlorine heptelidic acid (8), trichoderonic acid A (9), 16-(α-D-mannopyranosyloxy)isopimar-7-en-19-oic acid (10), 16-(α-D-glucopyranosyloxy)isopimar-7-en-19-oic acid (11), 5-carboxymellein (12), and naphthalen-1,8-diol 1-O-α-D-glucopyranoside (13) have been isolated from the solid culture of the ascomycete fungus Xylaria sp. associated with termite nest. The structures of these compounds were elucidated primarily by NMR experiments. The absolute configurations of compounds 1-3 and 5-9 were determined by combination of X-ray data and CD spectral analysis. The absolute configuration of 4 was assigned by Snatzke's method. Compounds 8 and 11 showed slight cytotoxicities against two cell lines A549 and SGC7901.     

Six New Constituents from the Fruit of Hypericum patulum and Their Anti-Inflammatory Activity

Four new xanthone glucosides, 3-hydroxy-2-methoxyxanthone-4-O-β-D-glucopyranoside ( 1 ), 4,8-dihydroxy-2-methoxyxanthone-3-O-β-D-glucopyranoside ( 2 ), 2-methoxyxanthone-5-O-β-D-glucopyranoside ( 3 ), 4-hydroxy-2-methoxyxanthone-3-O-β-D-glucopyranoside ( 4 ), a new phenolic acid, 4,4′-dihydroxy-3,3′-imino-di-benzoic acid monomethyl ester ( 5 ), and a new isoquinoline, methyl 6-hydroxy-1-oxo-1,2,3,4-tetrahydroisoquinoline-4-carboxylate ( 6 ) were isolated from the fruit of Hypericum patulum. The structural elucidation of the isolated compounds was primarily based on HR-ESI-MS, UV, IR, 1D and 2D NMR. All compounds were evaluated for their inhibitory effect against LPS-induced NO production in RAW 264.7 cells. Compound 2 , 3 exhibited moderate inhibitory activity against NO production.     

Cytotoxic isoflavones from Erythrina indica.

Bioassay-directed fractionation of the CH(2)Cl(2)-MeOH (1:1) extract of the stem bark of Erythrina indica, has resulted in the isolation of two new isoflavone derivatives named indicanines D and E together with 11 known compounds including: six isoflavones (genistein, wighteone, alpinumisoflavone, dimethylalpinumisoflavone, 8-prenyl erythrinin C, and erysenegalensein E), one cinnamate (erythrinassinate B), two pentacyclic triterpenes (oleanolic acid and erythrodiol), and two phytosterols (stigmasterol and its 3-O-beta-D-glucopyranoside). The structures of the new compounds were elucidated by means of spectroscopic analysis. The in vitro cytocidal activity against KB cells of some of the isolated compounds is also reported.     

Diosgenin glucuronides from Solanum lyratum and their cytotoxicity against tumor cell lines

Bioassay-directed fractionation of the cytotoxicity active fraction of the whole plant from Solanum lyratum led to the isolation of a new steroidal saponin, diosgenin 3-O-beta-D-glucopyranosiduronic acid methyl ester (2), as well as four known compounds, diosgenin (1), diosgenin 3-O-beta-D-glucopyranosiduronic acid (3), diosgenin 3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranosiduronic acid (4), diosgenin 3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucuroniduronic acid methyl ester (5). The structures of the isolated compounds were elucidated on the basis of their spectral data and chemical evidences. Compound 1 was isolated for the first time from this plant, and compound 3 was isolated as a new natural product. Cytotoxic activities of the isolated compounds were evaluated and the cytotoxicities of compounds 2-5 reported for the first time.     

Glycosides from Roots of Cyathula officinalis Kuan

Abstract: To search for new and bioactive compounds from traditional Chinese medicines, a new glycoside, 3-O-[α- L -rhamnopyranosyl-(1→3)-( n -butyl-β- D -glucopyranosiduronate)]-28-O-β- D -glucopyranosyloleanolic acid ( 1 ), was isolated from the roots of Cyathula officinalis Kuan, along with 3-O-(methyl-β- D -glucopyranosiduronate)-28-O-β- D -glucopyranosyl oleanolic acid ( 2 ), 3-O-β- D -glucopyranosyl oleanolic acid ( 3 ), 3-O-β- D -glucuronopyranosyl oleanolic acid ( 4 ), 3-O-[β- L -rhamnopyranosyl-(1→3)-(β- D -glucuronopyranosyl)] oleanolic acid ( 5 ), 3-O-(β- D -glucuronopyranosyl)-28-O-β- D -glucopyranosyl oleanolic acid ( 6 ), 28-O-β- D -glucuronopyranosyl-(1→4)-β- D -glucopyranosyl hederagenin ( 7 ), 3-O-[β- L -rhamnopyranosyl-(1→3)-β- D -glucuronopyranosyl]-28-O-β- D -glucopyranosyl oleanolic acid ( 8 ), and 3-O-[β- D -glucopyranosyl-(1→2)-α- L -rhamnopyranosyl-(1→3)-β- D -glucuronopyranosyl]-28-O-β- D -glucopyranosyl oleanolic acid ( 9 ). The structures of these compounds were determined based on spectral and chemical evidence. The 50 per cent growth-inhibiting (GI₅₀) of compounds 1 and 5 against MDA-MB-231 (a human breast cancer cell line) was 3.44 × 10^-4 and 4.66 × 10^-4 mol/L, respectively.
(Managing editor: Wei WANG)     

Three New Constituents with Anti-Inflammatory and Antimicrobial Activities in Vitro from the Roots of Capsicum annuum L.

Three new compounds, including two new sesquiterpenes ( 1–2 ), named Annuumine E−F, and one new natural product, 3-hydroxy-2,6-dimethylbenzenemethanol ( 3 ), together with seventeen known compounds ( 4–20 ) were isolated from the ethanol extract of the roots of Capsicum annuum L. Among them, five compounds ( 4 , 5 , 9 , 10 and 20 ) were isolated from this plant for the first time. The structures of new compounds ( 1–3 ) were determined via detailed analysis of the IR, HR-ESI-MS and 1D and 2D NMR spectra. The anti-inflammatory activities of the isolated compounds were evaluated by their ability to reduce NO release by LPS-induced RAW 264.7 cells. Notably, compound 11 exhibited moderate anti-inflammatory activity (IC₅₀=21.11 μM). Moreover, the antibacterial activities of the isolated compounds were also evaluated.     

A sugar ester and an iridoid glycoside from Scrophularia ningpoensis

From cytotoxic extracts of the roots of Scrophularia ningpoensis Hemsl. (Scrophulariaceae) a new sugar ester, ningposide D (3-O-acetyl-2-O-p-methoxycinnamoyl-alpha(beta)-L-rhamnopyranose) (1) and a new iridoid glycoside, scrophuloside B4 (6-O-(2'-O-acetyl-3'-O-cinnamoyl-4'-O-p-methoxycinnamoyl-alpha-L-rhamnopyranosyl) catalpol) (2) along with known compounds: oleanonic acid (3), ursolonic acid (4), cinnamic acid (5), 3-hydroxy-4-methoxy benzoic acid (6), 5-(hydroxymethyl)-2-furfural (7) and beta-sitosterol (8) were isolated. The structures of the new compounds were elucidated by spectral data (1, 2D NMR, EI, HRESI-MS and MS/MS). Oleanonic acid (3) and ursolonic acid (4) were found to be cytotoxic against a series of human cancer cell lines with IC50=4.6, 15.5 microM on MCF7; 4.2, 14.5 microM on K562; 14.8, 44.4 microM on Bowes; 24.9, 43.6 microM on T24S; 61.3, 151.5 microM on A549, respectively. Beta-sitosterol (8) inhibited Bowes cells growth at IC50=36.5 microM. Scrophuloside B4 (2) showed activity on K562 and Bowes cells at IC50=44.6, 90.2 microM, respectively.     

草果果实中的酚性成分

从草果( Amomum tsao-ko) 果实的甲醇提取物中分离得到了9 个酚性化合物, 其中一个为新的糖基被酰化的酚性配糖体。用1D, 2D NMR 和MS 等现代波谱学方法鉴定为2-甲氧基-1 , 4-二苯酚-1-O - [6- O -(3-甲氧基-4-羟基苯甲酰基) ]-β-D-吡喃葡萄糖苷(1) 。8 个已知化合物分别为3′, 5′-二-C-β-D-吡喃葡萄糖基根皮素( 2)、芦丁(3) 、槲皮素-3- O-β-D-吡喃葡萄糖苷(4 ) 、邻苯三酚( 5 )、邻苯二酚( 6) 、对羟基苯甲酸( 7)、原儿茶酸(8) 和香草酸(9) 。化合物2 , 3 , 5 , 7～9 均为首次从草果果实中分离得到。     

Studies on the Constituents of Aristolochia versicolar S. M. Hwang

Twenty-four constituents were isolated from the root of Aristolochia versicolar S. M. Hwang (collected from Guangxi province, China). Ten of them (two novel sesquiterpene lacrones and eight known compounds) were reported recently. This paper deals with the other eight compounds. From the petroleum ether extraction a sesquiterpene lactone, C15H20O2, mp. 94–95℃ [α]D36 –49˚ (C=1.8, EtOH), confirmed to be isoaristolactone, was obtained from plants for the first time. On the basis of spectral analysis (UV, IR, 1HNMR, 13CNMR, MS) and chemical reactions its structure was determined as B2. From the petroleum enter unsoluble sec- tion 6-methoxyaristolic acid methyl ester (D1), aristolic acid (D3), 6-methoxyaristolic acid (ari- stolinic acid) (D4f), 6-methoxyaristolochic acid methyl ester (D4y), aristolochic acid A(D5), β-sitosterol-D-glucoside (D10) and allantoin (C2) were isolated and identified. Dx, Ds, and Ds show ed antifertility activity in mice.     

Triterpenoid saponins from Pteleopsis suberosa stem bark

Thirteen oleanane saponins (1-13), four of which were new compounds (1-4), were isolated from Pteleopsis suberosa Engl. et Diels stem bark (Combretaceae). Their structures were determined by 1D and 2D NMR spectroscopy and ESI-MS spectrometry. The compounds were identified as 2alpha,3beta,19alpha,23,24-pentahydroxy-11-oxo-olean-12-en-28-oic acid 28-O-beta-D-glucopyranosyl ester (1), 2alpha,3beta,19beta,23,24-pentahydroxy-11-oxo-olean-12-en-28-oic acid 28-O-beta-D-glucopyranosyl ester (2), 2alpha,3beta,19alpha,23-tetrahydroxy-11-oxo-olean-12-en-28-oic acid 28-O-beta-D-glucopyranosyl ester (3), and 2alpha,3beta,6beta,19alpha,24-pentahydroxy-11-oxo-olean-12- en-28-oic acid 28-O-beta-D-glucopyranosyl ester (4). The presence of alpha,beta-unsaturated carbonyl function was not common in the oleanane class and the aglycons of these compounds were not found previously in the literature. Moreover, the isolated compounds were tested against Helicobacter pylori standard and vacA, and cagA clinical virulence genotypes. Results showed that compound 6 has an anti-H. pylori activity against three metronidazole-resistant strains (Ci 1 cagA, Ci 2 vacA, and Ci 3).     

Two new saponins from Paronychia capitata

Two new oleanane-type triterpene glycosides, 3˗O˗β˗D˗glucopyranosyl˗28˗O˗[β˗D˗glucopyranosyl˗(1→2)˗β˗D˗xylopyranosyl˗(1→6)˗β˗D˗glucopyranosyl]medicagenic acid (1) and 3˗O˗β˗D˗glucopyranosyl˗28˗O˗[β˗D˗glucopyranosyl˗(1→6)˗β˗D˗glucopyranosyl˗(1→2)˗ β˗D˗xylopyranosyl]oleanolic acid (2), named capitatosides A and B respectively, were isolated from the butanol extract of Paronychia capitata (L.) Lam., along with seven known compounds. The structures of the isolated compounds were established by spectroscopic methods, mainly HRMS, 1D and 2D NMR (¹H, ¹³C, COSY, HSQC, HMBC and NOESY) techniques, whereas those of the known compounds were identified by spectral comparison with reported literature data.     

Free radical scavengers from the medicinal mushroom Inonotus xeranticus and their proposed biogenesis

New free radical scavengers, inoscavin D (1) and methylinoscavin D (2), were isolated from the methanolic extract of the fruiting bodies of Inonotus xeranticus (Hymenochaetaceae), along with the known compounds phelligridin D (3), 3,4-dihydroxybenzaldehyde (4), and 3,4-dihydroxybenzoic acid (5). Their structures were established by various spectroscopic analyses. Compounds 1 and 3 were proposed to be biosynthesized from the oxidative coupling of the precursor hispidin with 3,4-dihydroxybenzaldehyde and 3,4-dihydroxybenzoic acid, respectively. These compounds exhibited significant scavenging activity against the ABTS radical cation, and compounds 2 and 4 displayed moderate superoxide radical scavenging activity.     

Chemical Constituents from the Whole Plant of Gaultheria itoana Hayata

Two new diterpenoids, 14,18‐dihydroxyabieta‐8,11,13‐trien‐7‐one ( 1 ) and 13‐acetyl‐14,18‐dihydroxy‐podocarpa‐8,11,13‐triene ( 2 ), together with eight known compounds, i.e., gaultheric acid ( 3 ), vanillic acid ( 4 ), 4‐hydroxybenzoic acid ( 5 ), cinnamic acid ( 6 ), stearic acid ( 7 ), palmitic acid ( 8 ), β‐sitosterol ( 9 ), and stigmasterol ( 10 ), were isolated from the MeOH extract of the whole plant of Gaultheria itoana Hayata (Ericaceae). The structures of the new constituents were elucidated by spectroscopic methods (UV, IR, and 1D‐ and 2D‐NMR) and by mass spectrometry (HR‐ESI‐MS). Among them, 1 and 2 were demonstrated to exhibit significant cytotoxic activity against the LNCaP cell line.     

Two ellagitannins from Punica granatum heartwood

In the course of studies on polyphenol metabolism in Punica granatum heartwood two new ellagitannins, diellagic acid rhamnosyl (1-->4) glucopyranoside and 5-O-galloylpunicacortein D were isolated and characterized together with four known tannin metabolites, punicacortein D, punicalin, punicalagin and 2-O-galloylpunicalin. Structures of the isolated compounds were established by chromatography, chemical degradation, UV and 1D/ 2D 1H/13C NMR spectroscopy.     

Dihydroagarofuran alkaloid and triterpenes from Maytenus heterophylla and Maytenus arbutifolia

The antimicrobially active EtOH extracts of Maytenus heterophylla yielded a new dihydroagarofuran alkaloid,1beta-acetoxy-9alpha-benzoyloxy-2beta,6alpha-dinicotinoyloxy-beta-dihydroagarofuran, together with the known compounds beta-amyrin, maytenfolic acid, 3alpha-hydroxy-2-oxofriedelane-20alpha-carboxylic acid, lup-20(29)-ene-1beta,3beta-diol, (-)-4'-methylepigallocatechin, and (-)-epicatechin. In addition, beta-amyrin, (-)-epicatechin and (-)-4'-methylepigallocatechin were isolated from Maytenus arbutifolia. The structure elucidation of the isolated compounds was based primarily on 1D and 2D NMR analyses, including HMQC, HMBC, and NOESY correlations. Maytenfolic acid showed moderate antimicrobial activity by inhibiting the growth of Candida albicans, Cryptococcus neoformans, Staphylococcus aureus and Pseudomonas aeruginosa.