Coumarins from campylotropis hirtella (FRANCH.) SCHINDL. and their inhibitory activity on prostate specific antigen secreted from LNCaP cells

Campylotropis hirtella (FRANCH.) SCHINDL. was used as a folk medicine for the treatment of benign prostate hyperplasia (BPH) in China. In this study, two new coumarins, 7,2',4'-trihydroxy-5-methoxy-3-arylcoumarin (1), 6-[(1S,2S)-2-angeloyloxy-1,3-dihydroxy-3-methylbutyl]-7-methoxycoumarin, named angelol M (2), together with eleven known related compounds (3-13) were isolated from this plant under the bioassay guided fractionation. All the compounds showed activity with different levels in inhibiting prostate specific antigen (PSA) secreted from androgen dependent prostate cancer cell line, LNCaP cells, using ELISA method.     

Synthesis of hydrophilic and lipophilic 4-arylcoumarin phosphates

Novel hydrophilic and lipophilic prodrugs, sodium 4-arylcoumarin dialkylphosphates and 4-arylcoumarin dioleyl phosphates, were synthesized by phosphorylation of 4-arylcoumarins with dialkylphosphites.     

Modified coumarins. 29. Synthesis of structural analogs of natural 6-arylfuro[3,2-<Emphasis Type="Italic">g</Emphasis>]chromen-7-ones

3-Substituted 6-arylfuro[3,2-g]chromen-7-ones, structural analogs of natural furocoumarins, were synthesized by linear annelation of a furan fragment to a 3-arylcoumarin system. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 140–144, March–April, 2009.     

The isolation and structure elucidation of minor isoflavonoids from licorice of Glycyrrhiza glabra origin

Two new isoflavanone and one new 3-arylcoumarin derivatives, along with a known compound 3,4-didehydroglabridin, were isolated from commercially available licorice of Glycyrrhiza glabra origin, and their structures were elucidated on the basis of both the chemical and spectroscopic evidence.     

Novel water-soluble anticancer agents derived from 4-arylcoumarins

Novel 4-arylcoumarin derivatives were obtained. They are water-soluble analogs of the well-known anticancer drug combretastatin A-4. The key step of the synthesis involves the Suzuki-Miyaura cross-coupling. The water-soluble salts obtained exhibit considerable cytotoxic activity against the HBL-100 and HaCaT cell lines.     

Structures of 4-aryl-coumarin (neoflavone) dimers isolated from Pistacia chinensis BUNGE and their estrogen-like activity

Activity-guided fractionation of twigs of Pistacia chinensis resulted in the isolation and characterization of two novel ingredients as potent estrogen agonists. On the basis of spectral analysis and comparison with a related compound their structures were elucidated as 3,3'-dimers of 4-aryldihydrocoumarins (3,4-dihydro-4-(4'-hydroxyphenyl)-7-hydroxycoumarin) differing only in the stereochemical disposition of the linkage between the two 4-arylcoumarin moieties. These compounds are the first examples of bis-flavonoids which have been proven to possess estrogen-like activity.     

Preparation of three positional isomers of diglucosyl-cyclomaltohexaose.

Three positional isomers of diglucosyl-cyclomaltohexaose (diglucosyl-cG6) were chemically synthesized via 6(1),6(2)-, 6(1),6(3)-, and 6(1),6(4)-di-O-(TERT-butyldimethylsilyl)-cG6S (1, 2, and 3) prepared regiospecifically. Glucosylation of bis(2,3-di-O-acetyl)tetrakis(2,3,6-tri-O-acetyl)-CG6S obtained from the three regioisomeric compounds 1, 2, and 3 with 2,3,4,6-tetra-O-benzyl-1-O-trichloroacetimidoyl-alpha-D-glucopyran ose, followed by debenzylation and then deacetylation, afforded 6(1),6(2)-, 6(1),6(3)-, and 6(1),6(4)-di-O-(alpha-D-glucopyranosyl)-cG6S (10, 11, and 12) together with configurational isomers. The desired compounds 10, 11, and 12 containing two (1----6)-alpha-linkages were isolated from the mixtures of their configurational isomers by high performance liquid chromatography. The three diglucosyl-cG6S synthesized chemically were used as authentic samples to identify the components in a mixture of diglucosyl-cG6S produced by an enzymatic process.     

Syntheses and reactions of hexavalent organotellurium compounds bearing five or six tellurium-carbon bonds

A variety of hexaorganotellurium compounds, Ar(6-n)(CH3)nTe [Ar=4-CF3C6H4, n=0 (1a), n=1 (3a), n=2 (trans-4a and cis-4a), n=3 (mer-5a), n=4 (trans-6a); Ph, n=0 (1b), n=1 (3b), n=2 (trans-4b); 4-CH3C6H4, n=0 (1c), n=1 (3c), n=2 (trans-4c), n=4 (trans-6c); 4-BrC6H4, n=0 (1d)] and Ar5(R)Te [Ar=4-CF3C6H4, R=4-CH3OC6H4 (8); Ar=4-CF3C6H4, R=vinyl (9), Ar=Ph, R=vinyl (10), Ar=4-CF3C6H4, R=PhSCH2 (11), Ar=Ph, R=PhSCH2 (12), Ar=4-CF3C6H4, R=nBu (13)] and pentaorganotellurium halides, Ar5TeX [Ar=4-CF3C6H4, X=Cl (2a-Cl), X=Br (2a-Br); Ar=Ph, X=Cl (2b-Cl), X=Br (2b-Br); Ar=4-CH3C6H4, X=Cl (2c-Cl), X=Br (2c-Br); Ar=4-BrC6H4, X=Br (2d-Br)] and (4-CF3C6H4)4(CH3)TeX [X=Cl (trans-7a-Cl) and X=Br (trans-7a-Br)] were synthesized by the following methods: 1) one-pot synthesis of 1 a, 2) the reaction of SO2Cl2 or Br2 with Ar5Te(-)Li+ generated from TeCl4 or TeBr4 with five equivalents of ArLi, 3) reductive cleavage of Ar(6-m)(CH3)(m)Te (m=0 or 2) with KC8 followed by treatment with CH3I, 4) valence expansion reaction from low-valent tellurium compounds by treatment with KC8 followed by reaction with CH3I, 5) nucleophilic substitution of Ar(6-y-z)(CH3)zTeX(y-z) (X=Cl, Br, OTf; z=0, 1; y=1, 2) with organolithium reagents. The scope and limitations and some details for each method are discussed and electrophilic halogenation of the hexaorganotellurium compounds is also described.     

New sesquiterpenes and calebin derivatives from Curcuma longa

One novel sesquiterpene with new skeleton, (6S)-2-methyl-6-(4-hydroxyphenyl-3-methyl)-2-hepten-4-one (1), two new bisabolane sesquiterpenes, (6S)-2-methyl-6-(4-hydroxyphenyl)-2-hepten-4-one (2), (6S)-2-methyl-6-(4-formylphenyl)-2-hepten-4-one (3), and two calebin derivatives, 4'-(4'-hydroxyphenyl-3'-methoxy)-2'-oxo-3'-butenyl-3-(4'-hydroxyphenyl)-propenoate (4) and 4'-(4'-hydroxyphenyl)-2'-oxo-3'-butenyl-3-(4'-hydroxyphenyl-3'-methoxy)-propenoate (5) were isolated along with five known bisabolane sesquiterpenes from Curcuma longa. 1-4 were new compounds and 5 was a new natural product. Their structures were established by spectral methods.     

Cholinesterase inhibiting withanolides from Withania somnifera

A total of two new (1, 2) and four known (3-6) withanolides were isolated from the whole plant of Withania somnifera. Their structures were elucidated on the basis of spectroscopic techniques and were characterized as 6alpha,7alpha-epoxy-3beta,5alpha,20beta-trihydroxy-1-oxowitha-24-enolide (1), 5beta,6beta-epoxy-4beta,17alpha,27-trihydroxy-1-oxowitha-2,24-dienolide (2), withaferin-A (3), 2,3-dihydrowithaferin-A (4), 6alpha,7alpha-epoxy-5alpha,20beta-dihydroxy-1-oxowitha-2,24-dienolide (5), and 5beta,6beta-epoxy-4beta-hydroxy-1-oxowitha-2,14,24-trienolide (6), respectively. Compounds 2, 3, 5, and 6 displayed inhibitory potential against butyrylcholinesterase, but only compounds 3, 4, and 6 were found to be active against acetylcholinesterase.     

Phenolic constituents from the rhizomes of Dryopteris crassirhizoma

A new phenolic glycoside, dryopteroside (1), was isolated from the rhizomes of Dryopteris crassirhizoma (Dryopteridaceae), together with five known compounds, 4beta-carboxymethyl-(-)-epicatechin (2), isobiflorin (3), biflorin (4), 1-beta-D-glucopyranosyloxy-3-methoxy-5-hydroxybenzene (5) and (+)-catechin-6-C-beta-D-glucopyranoside (6). The new compound was elucidated to be 1-butanoyl-3-C-beta-D-glucopyranosyl-5-methyl-phloroglucinyl-6-O-beta-D-glucopyranoside (1) by chemical and various spectroscopic analyses. The known compounds 2-6 were first reported from the genus Dryopteris.     

Five new phenylethanoid glycosides from the whole plants of Lamium purpureum L

Five new phenylethanoid glycosides, lamiusides A (1), B (2), C (3), D (4) and E (5), were isolated from the whole plants of Lamium purpureum L. (Labiatae) together with seven known compounds (6-12). On the basis of chemical and spectral analyses, the structures of the new compounds were elucidated to be 2-(3,4-dihydroxyphenyl)ethyl-O-beta-D-galactopyranosyl-(1-->2)-alpha-L-rhamnopyranosyl-(1-->3)-(4-O-trans-caffeoyl)-beta-D-glucopyranoside (1), 2-(3,4-dihydroxyphenyl)ethyl-O-beta-D-galactopyranosyl-(1-->2)-alpha-L-rhamnopyranosyl-(1-->3)-(4-O-trans-feruloyl)-beta-D-glucopyranoside (2), 2-(3,4-dihydroxyphenyl)ethyl-O-beta-D-galactopyranosyl-(1-->2)-alpha-L-rhamnopyranosyl-(1-->3)-(6-O-trans-caffeoyl)-beta-D-glucopyranoside (3), 2-(3,4-dihydroxyphenyl)-R,S-methoxy-ethyl-O-beta-D-galactopyranosyl-(1-->2)-alpha-L-rhamnopyranosyl-(1-->3)-(4-O-trans-caffeoyl)-beta-D-glucopyranoside (4) and 2-(3-hydroxy-4-methoxyphenyl)ethyl-O-alpha-L-rhamnopyranosyl-(1-->3)-beta-D-glucopyranosyl-(1-->6)-(4-O-cis-feruloyl)-beta-D-glucopyranoside (5). In addition, the radical-scavenging activities of compounds 1-4 on 1,1-diphenyl-2-picrylhydrazyl radical were examined.     

培养南海红树林内源真菌Fusarium sp. ZZF60产新型蒽醌衍生物

通过人工发酵培养,从南海红树林内源真菌Fusarium sp.ZZF60的培养液中分离得到:1种新蒽醌衍生物,6,8-二甲氧基-1-甲基-2-(3-氧丁基)蒽醌(1),以及5种已知化合物:7-羟基-3-(4-甲氧基苯基)苯并-γ-吡喃酮(2),2,4-二羟基-6-[(1′E,3′E)-1′,3′-戊二烯基]苯甲醛(3),(E)-4-羟基肉桂酸甲酯(4),4-(4-羟基苯基)-2-丁醇(5),4-羟基苯甲酸(6)。它们的结构通过MS、NMR等波谱分析推导确定。初步药理活性显示,化合物1抑制体外培养人喉癌细胞Hep2和人肝癌细胞HepG2的IC50分别为16和23μmol/L。     

Studies on Triterpenoid Glycosides from Rhizomes of Panacis majoris and Their Antiplatelet Aggregation Activity

A new triterpenoid glycoside(1) and seven known triterpenoid glycosides, pseudoginsenoside RT2(2), yesanchinoside R2(3), vinaginsenoside R13(4), vinaginsenoside R8(5), notoginsenoside E(6), 6'-O-acetylginsenoside Re(7), 6"-O-acetylginsenoside Rb₁(8), were isolated from the rhizomes of Panacis majoris. The new triterpenoid glycoside was elucidated as 3-O-[β-D-glucopyranosyl-(1→2)-β-D-(6'-O-ethyl)-glucuronopyranosyl]-oleanolic acid-28-O-β-D-glucopyranoside by extensive spectroscopic and phytochemical methods. Compounds 2-8 were obtained from the plant for the first time. Compounds 3 and 4 displayed good activities against adenosine diphosphate (ADP)-induced platelet aggregation, and compounds 1, 5, 6 and 8 showed moderate activities. Compound 6 exhibited moderate antiplatelet aggregation activity induced by arachidonic acid(AA).     

New abietane and seco-abietane diterpenes from the roots of Taiwania cryptomerioides

Four new diterpenes, 3-oxosaprorthoquinone (1), 3-oxomicrostegiol (2), 3-oxoisotaxodione (3), and taiwaninal (4), together with two known compounds, 3-oxosapriparaquinone (5) and 6-dehydrohinokiol (6), were isolated from the roots of Taiwania cryptomerioides. The structures of 1-4 were principle elucidated based on spectral evidence.     

New stilbenoids from Pholidota yunnanensis and their inhibitory effects on nitric oxide production

Six new stilbenoids, a (bibenzyldihydrophenanthrene) ether designated phoyunnanin D (1), a bis(dihydrophenanthrene) ether designated phoyunnanin E (2), and four stilbenes designated phoyunbene A-D (3-6), were isolated from the air-dried whole plant of Pholidota yunnanensis ROLFE. The new compounds were identified as 7-[2-(3-hydroxyphenethyl)-4-hydroxy-6-methoxyphenoxy]-4-hydroxy-2-methoxy-9,10-dihydrophenanthrene (1), 1-[(9,10-dihydro-4-hydroxy-2-methoxy-7-phenanthrenyl)oxy]-4,7-dihydroxy-2-methoxy-9,10-dihydrophenanthrene (2), trans-3,3'-dihydroxy-2',4',5-trimethoxystilbene (3), trans-3,4'-dihydroxy-2',3',5-trimethoxystilbene (4), trans-3,3'-dihydroxy-2',5-dimethoxystilbene (5), and trans-3-hydroxy-2',3',5-trimethoxystilbene (6) based on spectroscopic evidence. Furthermore, the inhibitory effects of compounds 1-6 on nitric oxide production in a murine macrophage-like cell line (RAW 264.7) activated by lipopolysaccharide and interferon-gamma were examined.     

巴戟天内生真菌Trichoderma spirale A725中两个新的聚酮类化合物(英文)

综合运用硅胶柱色谱、反相硅胶柱色谱、Sephadex LH-20凝胶柱色谱以及制备型高效液相色谱技术对药用植物巴戟天内生真菌Trichoderma spirale A725的次生代谢产物进行分离纯化,得到6个聚酮类化合物,采用多种现代波谱技术确定其结构,分别为:6-羟基-4-异丙基-1,8-二甲基螺环[4.5]癸-1,8-二烯-7-酮(1),2-羟基-2,5-二甲基-7-氧代-5,7-二氢-2H-呋喃[3,4-b]吡喃-4-羧酸(2), 3-乙基-4-羟基-6-甲基-二氢-吡喃-2-酮(3),苯乙内酯A (4), 3-羟基-5-(4-羟基苄基)二氢呋喃-2(3H)-酮(5), 4-乙酰-3-羟基-6-甲基吡喃-2-酮(6).其中化合物1和2为新化合物,化合物3为新天然产物.此外,利用四株肿瘤细胞株(Hep G-2、MCF-7、SF-268及A549)对化合物1~6细胞毒活性进行评估,结果表明化合物1~6对上述肿瘤细胞均无明显的细胞毒活性.     

Prenylisoflavone derivatives from the roots of Hedysarum scoparium

Four new prenylisoflavone derivatives, namely, 5-hydroxy-4'-methoxy-8-prenyl-2'-hydroxyisopropyldihydrofurano[4,5:6,7]-isoflavone (1), 5-hydroxy-4'-methoxy-6-prenyl-2'-hydroxyisopropyldihydrofurano[4,5:8,7]-isoflavone (2), 5-hydroxy-4'-methoxy-8-prenyl-1',2'-peroxyl-3',3'-dimethyldihydropyrano[5,6:6,7]-isoflavone (3), and 5-hydroxy-4'-methoxy-6-prenyl-1',2'-peroxyl-3',3'-dimethyldihydropyrano[5,6:8,7]-isoflavone (4), together with three known ones 5-7, were isolated from the roots of Hedysarum scoparium. Their structures were established by means of detailed spectroscopic analysis (IR, EI- or HR-ESI-MS as well as 1D- and 2D-NMR), and by comparison of their spectroscopic data with those reported for structurally related compounds.     

Template synthesis of lanthanide (Pr, Nd, Gd) coordination polymers with 2-hydroxynicotinic acid exhibiting ferro-/antiferromagnetic interaction

Lanthanide coordination polymers were synthesized from Pr(III), Nd(III), and Gd(III) salts; 2-hydroxynicotinic acid (Hnica); and MnSO 4.H 2O under hydrothermal conditions. In the absence of (CH 3) 3CCOONa, 1D polymers with an infinite Ln(III)-O-Ln(III) chain structure, [Pr(Hnica)(H 2O) 2SO 4] n ( 1), [Nd(Hnica)(H 2O) 2SO 4] n ( 2), and [Gd(Hnica)(H 2O) 2SO 4] n ( 3), were generated. When (CH 3) 3CCOONa was added to the synthetic systems, 2D coordination polymers {[Pr 3(Hnica) 6(H 2O) 9].3H 2O.SO 4.NO 3} n ( 4), {[Nd 3(Hnica) 6(H 2O) 9].3H 2O.SO 4.NO 3} n ( 5), and {[Gd(Hnica) 2(H 2O) 2]ClO 4.H 2O} n ( 6) were obtained. Complexes 4 and 5 both exhibit Kagome lattice structure, while 6 displays a rhombic grid structure. All complexes were characterized by elemental analysis, IR spectra, UV-vis spectra, and X-ray single-crystal diffraction. The variable-temperature magnetic susceptibility studies reveal ferromagnetic interactions between gadolinium(III) ions in 3 and 6 and antiferromagnetic interactions in 1, 2, 4, and 5.     

Rhodiolosides A-E, monoterpene glycosides from Rhodiola rosea

Five new monoterpene glycosides, rhodiolosides A-E (1-5), were isolated from the roots of Rhodiola rosea (Crassulaceae). Their structures were elucidated as (2E,6E,4R)-4,8-dihydroxy-3,7-dimethyl-2,6-octadienyl beta-D-glucopyranoside (1), (2E,4R)-4-hydroxy-3,7-dimethyl-2,6-octadienyl alpha-D-glucopyranosyl(1-->6)-beta-D-glucopyranoside (2), (2E,4R)-4-hydroxy-3,7-dimethyl-2,6-octadienyl beta-D-glucopyranosyl(1-->3)-beta-D-glucopyranoside (3), (2E,4R)-4,7-dihydroxy-3,7-dimethyl-2-octenyl beta-D-glucopyranoside (4), and (2E)-7-hydroxy-3,7-dimethyl-2-octenyl alpha-L-arabinopyranosyl(1-->6)-beta-D-glucopyranoside (5), on the basis of various spectroscopic analyses and chemical degradation.