New eremophilane sesquiterpenes from Cacalia ainsliaeflora

One known eremophilanolide, 3beta-angeloyloxy-8beta,10beta-dihydroxy-6beta-methoxyeremophilenolide (1) and seven new eremophiane sesquiterpenes, 3beta-angeloyloxy-6beta-ethoxy-8beta,10beta-dihydroxyeremophilenolide (2), 3beta,6beta-diangeloyloxy-10alpha-hydroxy-8alpha-methoxyeremophilenolide, 6beta-angeloyloxy-8beta,10beta-dihydroxy-3-oxo-eremophilenolide, 6beta,8beta,10beta-trihydroxy-3-oxo-eremophilenolide, 3beta-angeloyloxy-6beta,10beta-dihydroxy-eremophila-7(11),8(9)-dien-8,12-olide (6), 3beta-angeloyloxy-10beta-hydroxy-6beta-methoxy-eremophila-7(11),8(9)-dien-8,12-olide, 3beta-angeloyloxy-8-oxo-eremophila-6.9-dien-12-oic acid ethyl ester, were isolated from the roots of Cacalia ainsliaeflora. Their structures were elucidated by spectroscopic methods. Compounds 1, 2 and 6 were assayed against both Gram-positive and Gram-negative bacteria. No positive activities were observed.     

Bioactive terpenes from the roots of Chloranthus henryi

12,15-Epoxy-5alpha H,9beta H-labda-8(17),13-dien-19-oic acid (1) and 14-methoxy-15,16-dinor-5alpha H,9alpha H-labda-13(E),8(17)-dien-12-one (2), two new labdane-type diterpenes, and 1alpha-hydroxy-8,12-epoxyeudesma-4,7,11-triene-6,9-dione (3), one new eudesmane-type sesquiterpene, were isolated from Chloranthus henryi Hemsl, along with two known compounds, 8beta H-eudesma-4(14),7(11)-dien-12,8-olide (4) and 8beta-hydroxyeudesma-4(14),7(11)-dien-12,8-olide (5). Their structures were established by a combination of 1D- and 2D-NMR spectroscopic techniques. The new compounds 2, 3 and the known compound 4 exhibited antitumor activities against Hela and K562 human tumor cell lines.     

Eremophilane sesquiterpenes from Ligularia myriocephala

Five new eremophilenolides, 1beta-angeloyloxy-6beta,10beta-dihydroxy-8beta-methoxyeremophil-7(11)-en-8alpha,12-olide ( 1), 1beta-angeloyloxy-6beta,10alpha-dihydroxy-8alpha-methoxyeremophil-7(11)-en-8beta,12-olide ( 2), 1beta,6beta-diangeloyloxy-8beta,10beta-dihydroxyeremophil-(11)-en-8alpha,12-olide ( 3), 1beta,6beta-diangeloyloxy-8alpha,10 alpha-dihydroxyeremophil-7(11)-en-8beta,12-olide ( 4), 1beta-angeloyloxy-8-oxoeremophil-6,9-dien-12-oic acid methyl ester ( 5) and one known compound, 8beta,10beta-dihydroxyeremophilenolide ( 6) were isolated from the extract of the whole plant of Ligularia myriocephala Ling. Their structures and stereochemistry were elucidated by various spectroscopic methods including intensive 2D-NMR techniques (COSY, gHMQC, gHMBC and (1)H- (1)H NOESY) and HR-ESI-MS. A single-crystal X-ray experiment was performed for compound 1.     

New eremophilane-type sesquiterpenes from Ligularia hodgsonii

Four new eremophilanlides (1- 4) together with a known sesquiterpene were isolated from the roots and rhizomes of Ligularia hodgsonii. The structures of these new compounds were established as 6beta-(2'-methylbutanoyloxy)-10beta-acetoxy-3 beta, 8beta-dihydroxyeremophil-7(11)-en-8,12-olide (1), 6beta,10 beta-dihydroxyeremophil-7(11)-en-8alpha,12-olide (2), 3beta-acetoxy-6,9-dien-8-oxoeremophil-12-nor-11-ketone (3), and 3beta-acetoxy-6alpha, 8alpha-dihydroxyeremophil-7(11), 9-dien-8,12-olide (4) by means of mass, IR and NMR spectroscopy.     

Six new sesquiterpenes from Cacalia ainsliaeflora

Five new eremophilane sesquiterpenes, 3beta,6beta-diangeloyloxy-8beta,10beta-dihydroxyeremophilenolide (1); 6beta-acetoxy-3beta-angeloyloxy-8beta,10beta-dihydroxyeremophilenolide (2); 3beta-angeloyloxy-6beta-methoxyeremophil-7(11),9(10)-dien-8alpha,12-olide (3), 3beta-angeloyloxy-8-oxo-eremophil-6(7)-en-12-oic acid (4); 3beta-angeloyloxy-10beta-hydroxy-8-oxo-eremophil-6(7)-en-12-oic acid (5), and a novel nor-eremophilane derivative, 3beta-angeloyloxy-10beta-hydroxy-8-oxo-eremophil-6(7)-en (6), were isolated from the roots of Cacalia ainsliaeflora. Their structures were elucidated by spectroscopic methods, including 2DNMR. Compounds 1 and 2 were assayed against P388 and A549 Carcinoma cell lines. No positive activities were observed.     

Eremophilane sesquiterpene lactones from Ligularia virgaurea ssp. oligocephala

From an extract of the whole plant of Ligularia virgaurea ssp. oligocephala, three new eremophilane sesquiterpene lactones, 10alpha-hydroxy-1-oxoeremophila-7(11),8(9)-dien-12,8-olide (1), 6alpha,10alpha-dihydroxy-1-oxoeremophila-7(11),8(9)-dien-12,8-olide (2), 6beta,10beta-dihydroxyeremophila-7(11),8(9)-dien-12,8-olide (3), as well as four known sesquiterpene lactones with the same carbon skeleton, named toluccanolides A-C (4, 5, 7) and 6beta-hydroxy-8alpha-methoxyeremophila-1(10),7(11)-dien-12,8beta-olide (6) were isolated. Their structures were elucidated by spectroscopic methods including intensive 2D NMR techniques (gCOSY, gHMQC, gHMBC and 1H-1H NOESY for 2) and HR-ESI-MS.     

New eremophilane-type sesquiterpenes from Ligularia lapathifolia

Seven new eremophilanolides were isolated from the roots and rhizomes of Ligularia lapathifolia. Their structures were established as 3beta-angeloyloxy-8beta H-eremophil-7(11)-ene-12,8alpha (14beta, 6alpha)-diolide, 3beta-angeloyloxy-8beta-hydroxyeremophil-7(11)-ene-12,8alpha(14beta,6alpha)-diolide,3beta-angeloyloxy-8beta-methoxyeremophil- 7(11)-ene-12,8alpha(14beta,6alpha)-diolide,3beta-angeloyloxy-8beta-ethoxyeremophil-7(11)-ene-12, 8alpha (14beta,6alpha)-diolide, 3beta-angeloyloxy-10beta- hydroxyeremophil-8(9),7(11)-diene-12,8(14beta,6alpha)-diolide, 3beta-angeloyloxy-8,12-expoy-12alpha-hydroxy-8beta-methoxyeremophil-7(11)-en-14beta,6alpha-olide and 3beta-angeloyloxyeremophilan-7,11-dien-14beta,6alpha-olide, by means of spectroscopic analyses. Moreover, application of a photooxygenation reaction on 7 resulted in the generation of 2 with an alpha,beta-unsaturated gamma-lactone moiety. This biomimetic transformation supports a biogenetic pathway proposed for 2.     

New weakly cytotoxic eremophilane sesquiterpenes from the roots of Ligularia virgaurea

Six new eremophilane sesquiterpenes, including a novel nortrieremophilane carbon skeleton, were isolated from the roots of Ligularia virgaurea. Their structures were elucidated as 3 alpha,4 alpha-epoxy-6 alpha-(2'-methylacryloyl)oxy-8 alpha-methoxyeremophil-7(11)-en-8 beta,12-olide (1), 3 alpha,4 alpha-epoxy-6 alpha-(2'-methylacryloyl)oxy-8 alpha-ethoxyeremophil-7(11)-en-8 beta,12-olide (2), 1 beta,10 beta-epoxy-6 beta-(2'-methylacryloyl)oxy-8 beta-methoxyeremophil-7(11)-en-8 alpha,12-olide (3), 1 beta,10 beta-epoxy-6 beta-angeloyloxy-8 beta-methoxyeremophil-7(11)-en-8 alpha,12-olide (4), 6 beta-methoxyeremophil-7(11)-en-8 beta,12-olide (5), and 5 beta-angeloyloxy-3a,4,5,6,7,7a-hexahydro-3a beta-methyl-1 H-indene-2,4 beta-dioic acid methyl ester (6) by spectral methods, including IR, HR-ESI-MS, 1D and 2D NMR techniques. All of compounds were evaluated for their in vitro cytotoxic activities against human hepatoma (SMMC-7721), human promyelocytic leukemia (HL-60), and human hepatocyte (L-02) cells.     

Butyrylcholinesterase inhibitory guaianolides fromAmberboa ramosa

Phytochemical investigation of the whole plant of Amberboa ramosa led to the isolation of six sesquiterpene lactones which could be identified as 8alpha-hydroxy-11beta-methyl-1alphaH, 5alphaH, 6betaH, 7alphaH, 11alphaH-guai-10(14), 4(15)-dien-6, 12-olide(1), 3beta, 8alpha-dihydroxy-11alpha-methyl-1alphaH, 5alphaH, 6betaH, 7alphaH, 11betaH-guai-10(14), 4 (15)-dien-6, 12-olide (2), 3beta, 4alpha, 8alpha-trihydroxy-4beta-(hydroxymethyl)-1alphaH, 5alphaH, 6betaH, 7alphaH-guai-10(14), 11(13)-dien-6, 12-olide (3), 3beta, 4alpha, 8alpha-trihydroxy-4beta-(chloromethyl)-1alphaH, 5alphaH, 6betaH, 7alphaH-guai-10(14),11(13)-dien-6, 12-olide(4), 3beta, 4alpha, dihydroxy-4beta-(hydroxymethyl)-1alphaH, 5alphaH, 6betaH, 7alphaH-guai-10(14),11(13)-dien-6, 12-olide(5), 3beta, 4alpha-dihydroxy-4beta-(chloromethyl)-8alpha-(4-hydroxymethacrylate)-1alphaH, 5alphaH, 6betaH, 7alphaH-guai-10(14),11 (13)-dien-6,12-olide (6) by spectroscopic methods. All of them showed inhibitory potential against butyrylcholinesterase.     

Eremophilane-type sesquiterpenes from Senecio nemorensis

Three new highly oxygenated eremophilane-type sesquiterpenes, 1 beta,10 beta(8,12)-diepoxy-7 beta,11 beta-dihydroxy-8 beta,12 alpha-dimethoxyeremophilane (1), 1 beta,10 beta-epoxy-7 beta-hydroxy-8 alpha-methoxyeremophil-11 alphaH-12,8 beta-olide (2), and 6 beta-isobutyryloxy-8 alpha-hydroxy-1-oxoeremophil-7(11),9-dien-12,8 beta-olide (3), together with nine known compounds (4-12) were isolated from the roots and aerial parts of Senecio nemorensis L. (Compositae). Structures of compounds 1-3 were elucidated on the basis of spectroscopic evidence including IR, HR-ESI-MS, 1D and 2D NMR techniques and were unequivocally confirmed by single-crystal X-ray diffraction experiments. The antimicrobial activity of the isolated compounds 1-3 and 8-12 was tested against Staphylococcus aureus and Candida albicans.     

New guaiane, megastigmane and eudesmane-type sesquiterpenoids and anti-inflammatory constituents from Youngia japonica

Eleven sesquiterpenoids have been isolated from the whole plants of Youngia japonica (Asteraceae). Among these sesquiterpenoids, five were identified as new compounds on the basis of spectroscopic methods and chemical analysis. Their structures were 3-oxo-8alpha-(4-hydoxyphenyl)acetoxy-10(14),11(13)-guaiadien-12,6-olide ( 1), 3beta-[3-(4-hydroxyphenyl)acetyl-beta- D-glucopyranosyloxy]-8alpha-hydroxy-4(15),10(14),11(13)-guaiatrien-12,6-olide ( 2), 3beta-[3-(4-hydroxyphenyl)acetyl-beta- D-glucopyranosyloxy]-4(15),10(14),11(13)-guaiatrien-12,6-olide ( 3), 3alpha,5beta,6alpha-trihydroxy-4alpha-(beta- D-glucopyranosyloxy)-7-megastigmen-9-one ( 4), and 3alpha-(beta- D-glucopyranosyloxy)-4(15),11(13)-eudesmadien-12-oic acid ( 5). The three known components 3beta-(beta- D-glucopyranosyloxy)-8alpha-(4-hydroxyphenyl)acetoxy-4(15),10(14),11(13)-guaiatrien-12,6-olide ( 8), 3beta-(beta- D-glucopyranosyloxy)-4(15),10(14),11 (13)-guaiatrien-12,6-olide ( 9), and 3alpha-hydroxy-4alpha-(beta- D-glucopyranosyloxy)-5,7-megastigmadien-9-one ( 11) showed inhibitory activity against the proliferation of T and B lymphocytes of mice in vitro at concentrations of 1 x 10 ( - 7), 1 x 10 ( - 6), and/or 1 x 10 ( - 5) M without obvious cytotoxicity. Compound 9, the major component of the plant extract, exhibited weak anti-inflammatory activity at a dosage of 50 mg/kg ( p. o.) in in vivo anti-inflammatory experiments of mice.     

Inhibitory Constituents against Cyclooxygenases fromAralia cordata Thunb

Seven diterpenes, four polyacetylenes, a lipid glycerol, and two sterols were isolated from the methylene chloride fraction of the root of Aralia cordata. Their chemical structures were determined as (-)-pimara-8(14),15-dien-19-oic acid (2), pimaric acid (3), (-)-kaur-16-en-19-oic acid (4), 17-hydroxy-ent-kaur-15-en-19-oic acid (9), 7alpha-hydroxy-(-)-pimara-8(14),15-dien-19-oic acid (10), 16alpha,17-dihydroxy-(-)-kauran-19-oic acid (11), 16-hydroxy-17-isovaleroyloxy-ent-kauran-19-oic acid (12), falcarindiol (5), dehydrofalcarindiol (6), dehydrofalcarindiol-8-acetate (7), falcarindiol-8-acetate (8), alpha-mono palmitin (13), stigmasterol (1), and daucosterol (14) by the spectral evidences. These compounds were tested with COX-1 and COX-2 inhibition assays. This study found that compounds 2, 4, 5, 6, 7, 8, and 10 inhibited COX-1 dependent conversion of the exogenous arachidonic acid to PGE2 in a dose-dependent manner with IC50 values of 134.2 microM, 121.6 microM, 170 microM, 50.4 microM, 11.7 microM, 99.6 microM, and 69.6 microM, respectively. But, most of these compounds weakly inhibited COX-2 dependent PGE2 generation. Among them, only compound 4 showed relatively significant inhibitory activity (IC50: 127.6 microM).     

Sesquiterpene lactones from Inula hookeri

Four new sesquiterpene lactones, (1 S,5 R,6 S,7 S,8 R,9 R,10 S,11 S)-6-acetoxy-9-hydroxy-4-oxo-pseudoguai-2(3)-en-12,8-olide, (1 S,2 R,5 R,6 S,7 R,8 S,10 R)-6-acetoxy-2-ethoxy-4-oxo-pseudoguai-11(13)-en-12,8-olide, (1 S,2 R,5 R,6 S,7 R,8 S,10 R)-6-acetoxy-2-hydroxy-4-oxo-pseudoguai-11(13)-en-12,8-olide, and 14-acetoxy-1 β,5 α,7 αH-4 β-hydroxy-guai-9(10),11(13)-dien-12,8 α-olide, along with 26 known sesquiterpene lactones, were isolated from the whole plants of Inula hookeri C. B. Clarke. Their structures were established based on spectroscopic methods including HRESIMS, 1D and 2D NMR, and CD techniques. All compounds were evaluated for their cytotoxic activities against HepG2, HeLa, PC-3, and MGC-803 cell lines by CCK-8 assay. Some of the isolates, especiallly pseudoguaianolides and guaianolides, exhibited significant cytotoxicities against these four examined cell lines.     

Microbial transformation of neoandrographolide by Aspergillus niger (AS 3.739)

The biotransformation of neoandrographolide (1) was investigated by using Aspergillus niger (AS 3.739). Five products were obtained and identified as 8(17),13-ent-labdadien-16,15-olid-19-oic acid (2), 19-hydroxy-8(17),13-ent-labdadien-16,15-olide (3), 18-hydroxy-8(17),13-ent-labdadien-16,15-olid-19-oic acid (4), 3alpha-hydroxy-8(17),13-ent-labdadien-16,15-olid-19-oic acid (5) and 8beta,19-dihydroxy-ent-labd-13-en-16,15-olide (6) by spectroscopic and chemical means. Products 4, 5 and 6 are new compounds.     

Two new sesquiterpene lactones from Sarcandra glabra

Two new sesquiterpene lactones (1) and (2), along with three known sesquiterpenes, atractylenolide beta (3), chloranthalactone E (4), and ( - )-istanbulin A (5), were isolated from the whole plant of Sarcandra glabra. The structures of two new compounds were established as 8beta,9alpha-dihydroxyeudesman-4(15),7(11)-dien-8alpha,12-olide (1) and 8beta,9alpha-dihydroxylindan-4(5),7 (11)-dien-8alpha,12-olide (2) on the basis of spectroscopic analysis. Compound 3 was isolated from this genus for the first time.     

A secondary metabolite amberin from Amberboa ramosa

Amberin (1), a new sesquiterpene lactone, has been isolated from the ethyl acetate soluble fraction of Amberboa ramosa together with apigenin (2), jaseocidine (3), crysoeriol (4), and 3β, 8α-dihydroxy-11α-methyl-1αH, 5αH, 6βH, 7αH, 11βH-guai-10(14), 4 (15)-dien-6, 12-olide (5). The structures of the isolated compounds have been elucidated by 1D and 2D NMR spectroscopy.     

A new inositol derivative from Prenanthes macrophylla

A new chiro-inositol ester, 4-hydroxyphenylacetyl-3-d-chiro-inositol ester (1), was isolated from the whole plants of Prenanthes macrophylla Franch., along with 10 known compounds, 4-hydroxyphenylacetic acid (2), trans-ethyl caffeate (3), cis-ethyl caffeate (4), protocatechualdehyde (5), luteolin (6), luteolin-7-O-β-d-glucoside (7), 15-hydroxy-2-oxo-guai-3-en-1α,5α,6β,7α,10α,11βH-12,6-olide (8), 15-glucopyranosyloxy-2-oxo-guaia-3,11(13)-dien-1α,5α,6β,7α,10αH-12,6-olide (9), ursolic acid (10), and oleanolic acid (11). Their structures were elucidated on the basis of spectroscopic analyses including HR-ESI-MS, ESI-MS, (1)H and (13)C NMR, HSQC, HMBC, and ROESY, and chemical evidences.     

Diterpenoids from Turraeanthus mannii

Three new compounds, 15-acetoxy-12-hydroxy-16-methyl-labda-8(17),13E-diene (1), ent-labda-8(17),13-dien-15,16-olid-19-oic acid methyl ester (2), and 12-hydroxy-labda-8(17),13-dien-15,16-olide (3), together with two known compounds, 19-acetoxy-ent-labda-8(17),13-dien-15,16-olide (4), and 16-acetoxy-12,15-epoxy-15beta-hydroxy-labda-8(17),13(16)-diene (5) were isolated from the stem bark of Turraeanthus mannii (Meliaceae). The structures of compounds 1 - 3 were elucidated by analysis of the spectroscopic data. The crude methanol extract and compound 5 exhibited weak antibacterial and antifungal activity.     

Chemical constituents from Trichosanthes cucumeroides

One new triterpenoid, 3β-[(E)-caffeoyloxy]-D:C-friedooleana-7,9(11)-dien-29-oic acid (1) and nine known triterpenoidsidentified as cucurbitacin B (2), 23,24-dihydrocucurbitacin B (3), 23,24-dihydrocu-curbitacin D (4), cucurbitacin D (5), cucurbalsaminol A (6), 3-epi-isocucurbitacin D (7), curbitacin G (8), cucurbitacin J (9) and cucurbitacin I (10)were purified from Trichosanthes cucumeroides. Their structures were confirmed by spectroscopic data analysis and comparison with previous literature. All compounds were obtained from T.cucumeroides for the first time.     

Eremophilenolides and other constituents from the roots of Ligularia sagitta

Chemical investigation of the roots of Ligularia sagitta has resulted in the characterization of six eremophilenolides 6beta,8beta-dimethoxy-10beta-hydroxyeremophil-7(11)-en-12,8alpha-olide (1), 6beta-angeloyloxy-10beta-hydroxy-8beta-methoxyeremophil-7(11)-en-12,8alpha-olide (2), 6beta-(2'-methylbutanoyloxy)-10beta-hydroxy-8beta-methoxyeremophil-7(11)-en-12,8alpha-olide (3), 6beta-angeloyloxy-10beta-hydroxy-8alpha-methoxyeremophil-7(11)-en-12,8beta-olide (4), 6beta-(2'-methylbutanoyloxy)-10beta-hydroxy-8alpha-methoxyeremophil-7(11)-en-12,8beta-olide (5) and 8beta,10beta-dihydroxy-6beta-methoxyeremophil-7(11)-en-12,8alpha-olide (6), together with one monoterpene (3 R,4 R,6 S)-3,6-dihydroxy-1-menthene (7), two triterpenes lupeol (8) and ursolic acid (9), and beta-sitosterol (10). The structures of five new constituents (1-5) were elucidated by spectroscopic methods including 2D-NMR experiments. The compounds 1, 5 and 7 showed antibacterial activity by being assayed against Staphylococcus aureus, Bacillus subtilis and Escherichia coli.