Cycloartane triterpenes from Euphorbia tuckeyana

Investigation of the acetone extract of the whole plant of Euphorbia tuckeyana afforded a new cycloartane-type triterpene named as cyclotucanol. Its structure was established as cycloartane-24-methylene-3beta,25-diol (1). The known cycloartane triterpenes cycloeucalenol (2), 3beta-hydroxycycloart-25-en-24-one (3), cycloart-25-ene-3beta,24-diol (4), 25,26,27-trisnor-3beta-hydroxycycloartan-24-al (5) and cycloart-23-ene-3beta,25-diol (6) were also isolated and identified.     

Triterpenes from the spores of Ganoderma lucidum and their cytotoxicity against meth-A and LLC tumor cells

Six new highly oxygenated lanostane-type triterpenes, called ganoderic acid gamma (1), ganoderic acid delta (2), ganoderic acid epsilon (3), ganoderic acid zeta (4), ganoderic acid eta (5) and ganoderic acid theta (6), were isolated from the spores of Ganoderma lucidum, together with known ganolucidic acid D (7) and ganoderic acid C2 (8). Their structures of the new triterpenes were determined as (23S)-7beta,15alpha,23-trihydroxy-3,11-dioxolanosta-8, 24(E)-diene-26-oic acid (1), (23S)-7alpha,15alpha23-trihydroxy-3,11-dioxolanosta-8, 24(E)-diene-26-oic acid (2), (23S)-3beta3,7beta, 23-trihydroxy-11,15-dioxolanosta-8,24(E)-diene-26-oic acid (3), (23S)-3beta,23-dihydroxy-7,11,15-trioxolanosta-8, 24(E)-diene-26-oic acid (4), (23S)-3beta,7beta,12beta,23-tetrahydroxy-11,15-dioxolanos ta-8,24(E)-diene-26-oic acid (5) and (23S)-3beta,12beta23-trihydroxy-7,11,15-trioxolanosta-8,24(E )-diene-26-oic acid (6), respectively, by chemical and spectroscopic means, which included the determination of a chiral center in the side chain by a modification of Mosher's method. The cytotoxicity of the compounds isolated from the Ganoderma spores was carried out in vitro against Meth-A and LLC tumor cell lines.     

Constituents of the Vietnamese medicinal plant Orthosiphon stamineus

From the MeOH extract of the aerial part of Vietnamese Orthosiphon stamineus, five new isopimarane-type diterpenes [orthosiphols F-J (1-5)] and two new diterpenes [staminols A (6) and B (7)] with a novel carbon-framework, to which we proposed the name "staminane", and three new highly-oxygenated staminane-type diterpenes [staminolactones A (8) and B (9) and norstaminol A (10)1 were isolated. Moreover, staminolactone A (8) is 8,14-secostaminane-type and staminolactone B (9) is 13,14-secostaminane-type, while norstaminol A (10) is 14-norstaminen-type. Together with these new diterpenes, sixteen known compounds were also isolated and identified to be: 7,3',4'-tri-O-methylluteolin (11), eupatorin (12), sinensetin (13), 5-hydroxy-6,7,3',4'-tetramethoxyflavone (14), salvigenin (15), ladanein (16), tetramethylscutellarein (17), 6-hydroxy-5,7,4'-trimethoxyflavone (18), vomifoliol (19), aurantiamide acetate (20), rosmarinic acid (21), caffeic acid (22), oleanolic acid (23), ursolic acid (24), betulinic acid (25), and beta-sitosterol (26). All the isolated compounds were tested for their cytotoxicity towards highly liver metastatic murine colon 26-L5 carcinoma cells, and the new diterpenes, except for 4, and flavonoids (11, 12, 16, 18) showed cytotoxicity with an ED50 value between 10 and 90 microg/ml.     

Lanostane-type triterpenoids from Diospyros discolor

Four new lanostane-type triterpenes, 24-ethyl-3beta-methoxylanost-9(11)-en-25-ol (1), 3beta-methoxy-24-methylenelanost-9(11)-en-25-ol (2), 3beta-methoxy-25-methyl-24-methylenelanost-9(11)-en-21-ol (3) and 3beta-methoxy-24-methyllanosta-9(11),25-dien-24-ol (4) together with three known triterpenes, betulinaldehyde, betulinic acid methyl ester, and ursaldehyde have been isolated from the methanol extract of the twigs of Diospyros discolor. The structures of those new compounds were elucidated by spectroscopic methods.     

D:C-friedooleanane-type triterpenoids from Lagenaria siceraria and their cytotoxic activity

Four new D:C-friedooleanane-type triterpenes, 3 beta-O-(E)-feruloyl-D:C-friedooleana-7,9(11)-dien-29-ol (1), 3 beta-O-(E)-coumaroyl-D:C-friedooleana-7,9(11)-dien-29-ol (2), 3 beta-O-(E)-coumaroyl-D:C-friedooleana-7,9(11)-dien-29-oic acid (3), and methyl 2 beta,3 beta-dihydroxy-D:C-friedoolean-8-en-29-oate (6), together with five known triterpenes with the same skeleton, 3-epikarounidiol (4), 3-oxo-D:C-friedoolena-7,9(11)-dien-29-oic acid (5), bryonolol (7), bryononic acid (8), and 20-epibryonolic acid (9), were isolated from the methanol extract of the stems of Lagenaria siceraria. The structures of those compounds were elucidated using spectroscopic methods. Compounds 3 and 9 showed significant cytotoxic activity against the SK-Hep 1 cell line with IC50 values of 4.8 and 2.1 microg/ml, respectively. Based on these initially promising results, the two D:C-friedooleanane triterpenes merit further study as potential anticancer agents.     

New triterpene aldehydes,lucialdehydes A-C,from Ganoderma lucidum and their cytotoxicity against murine and human tumor cells

Three new lanostante-type triterpene aldehydes, named lucialdehydes A-C (1-3), were isolated from the fruiting bodies of Ganoderma lucidum, together with ganodermanonol (4), ganodermadiol (5), ganodermanondiol (6), ganodermanontriol (7), ganoderic acid A (8), ganoderic acid B8 (9), and ganoderic acid C1 (10). The structures of the new triterpenes were determined as (24E)-3 beta-hydroxy-5 alpha-lanosta-7,9(11),24-trien-26-al (1), (24E)-3,7-dioxo-5 alpha-lanosta-8,24-dien-26-al (2), and (24E)-3 beta-hydroxy-7-oxo-5 alpha-lanosta-8,24-dien-26-al (3), respectively, by spectroscopic means. The cytotoxicity of the compounds isolated from the ganoderma mushroom was tested in vitro against Lewis lung carcinoma (LLC), T-47D, Sarcoma 180, and Meth-A tumor cell lines. Lucialdehydes B, C (2, 3), ganodermanonol (4) and ganodermanondiol (6) showed cytotoxic effects on tested tumor cells. Of the compounds, lucialdehyde C (3) exhibited the most potent cytotoxicity against LLC, T-47D, Sarcoma 180, and Meth-A tumor cells with ED(50) values of 10.7, 4.7, 7.1, and 3.8 microg/ml, respectively.     

Novel A-seco-rearranged lanostane triterpenoids from Abies sachalinensis

From the needles of Abies sachalinensis, novel rearranged lanostane type triterpenes, 1-4, were isolated along with a known triterpene (5). The structures of the new compounds, 1-4, were elucidated to be 3,4-seco-8-(14-->13R)abeo-17,13-friedo-9beta-lanosta-4(28),7,14(30),22Z,24-pentaen-26,23-olide-3-oic acid, methyl 3,4-seco-8-(14-->13R)abeo-17,13-friedo-9beta-lanosta-4(28),7,14(30),22Z,24-penten-26,23-olide-3-oate, 3,4-seco-8(14-->13R)abeo-17,13-friedo-9beta-lanosta-4(28),7,14,22Z,24-pentaene-26,23-olide-3-oic acid and methyl 3,4-seco-8(14-->13R)abeo-17,13-friedo-9beta-lanosta-4(28),7,14,22Z,24-pentaene-26,23-olide-3-oate, respectively, by means of spectral experiments, especially two dimensional NMR spectroscopy, such as 1H-detected multiple quantum coherence (HMQC), 1H-detected heteronuclear multiple bond connectivity (HMBC) and 1H-1H-correlation spectroscopy (COSY) experiments. These new compounds have novel structures containing A-seco, rearranged spiro structure and a gamma-lactone conjugated with a diene. Some of these compounds showed potent antibacterial activity against gram positive bacteria.     

Cytotoxicity of triterpenes isolated from Aceriphyllum rossii

Bioassay-guided fractionation of a MeOH extract of the whole plant of Aceriphyllum rossii (Saxifragaceae) led to the isolation of two new triterpenes, 3alpha,23-isopropylidenedioxyolean-12-en-27-oic acid (1) and 23-hydroxy-3-oxoolean-12-en-27-oic acid (2), together with six known triterpenes, 3-oxoolean-12-en-27-oic acid (3), 3alpha-hydroxyolean-12-en-27-oic acid (4), beta-peltoboykinolic acid (5), aceriphyllic acid A (6), oleanolic acid (7), and gypsogenic acid (8). The structures of these compounds were elucidated on the basis of physicochemical and spectroscopic analyses. These compounds were evaluated for in vitro cytotoxicity against the K562 and HL-60 cell lines. Olean-12-en-27-oic acid derivatives (1-6) exhibited considerable cytotoxicity against K562 and HL-60 cell lines with IC(50) values ranging from 12.2 to 28.7 microM and from 12.1 to 25.8 microM, respectively.     

A new cerebroside from fruits of Ailanthus altissima Swingle

A new cerebroside and three known cycloartan triterpenes were isolated from fruits of Ailanthus altissima Swingle. Their structures were identified as 1-O-beta-D-glucopyranosyl-(2S, 3R, 4E, 9E)-2-(2'R-hydroxyhexadecenoy)-4, 9-octadecadiene-1, 3-diol (1), 9, 19-cyclolanost-23 (Z)-ene-3beta, 25-diol (2), cycloart-25-ene-3beta, 24R-diol (3), and cycloart-25-ene-3beta, 24S-diol (4) by means of chemical and spectroscopic analysis. Compounds 2, 3, and 4 were isolated from genus Ailanthus for the first time. The analgesic activity of 1 was also evaluated.     

Indonesian propolis: chemical composition, biological activity and botanical origin

From a biologically active extract of Indonesian propolis from East Java, 11 compounds were isolated and identified: four alk(en)ylresorcinols (obtained as an inseparable mixture) (1-4) were isolated for the first time from propolis, along with four prenylflavanones (6-9) and three cycloartane-type triterpenes (5, 10 and 11). The structures of the components were elucidated based on their spectral properties. All prenylflavanones demonstrated significant radical scavenging activity against diphenylpicrylhydrazyl radicals, and compound 6 showed significant antibacterial activity against Staphylococcus aureus. For the first time Macaranga tanarius L. and Mangifera indica L. are shown as plant sources of Indonesian propolis.     

Chemical constituents from Aphanamixis grandifolia

(23E)-25-Methylcycloart-23-en-3β-ol (1), a cycloartane-type triterpenoid featuring an unusual skeleton of 31 carbon atoms, (17E)-cycloart-17,26-dien-3β-ol (2), a new cycloartane-type triterpenoid, and the other two new compounds 4R-hydroxy-4-(9S-hydroxy-12-methylhexan-6-yl)-3-methylcyclopent-2-enone (6) and 7-hydroxy-5-(2'-hydroxy-4',5'-dimethoxyphenyl)-2-methoxy-6-methyl-1,4-naphthoquinone (7), together with three known cycloart-3β-ol triterpenoids (3-5) were isolated from aerial parts of Aphanamixis grandifolia. Their structures were elucidated by spectroscopic analysis, and that of 1 was confirmed by single-crystal X-ray diffraction. The absolute configuration of two carbon stereocenters of compound 6 was determined to be 4R,9S by means of circular dichroism (CD) and auxiliary chiral α-methoxy-α-(trifluoromethyl)phenylacetic acid (MTPA) derivatives, respectively. The compound 3 exhibited significant cytotoxicities against HL-60, Hep G2 and HeLa, and compounds 1, 2, 5, 6 and 7 exhibited modest cytotoxicities. No activity of compound 4 could be due to the absence of the hydroxyl group at C-24.     

Polyhydroxylated steroids and other constituents of the soft coral Nephthea chabroli

Polyhydroxylated steroids and other metabolites were isolated from the soft coral Nephthea chabroli collected in South China Sea. The structures of two new compounds were determined to be 24-methylcholesta-9(11), 24(28)-diene-3beta,12alpha,19-triol and 4alpha-methyl-3beta,14beta-dihydroxy-5alpha-ergost-24(28)-en-23-one on the basis of spectroscopic analysis. Cytotoxic activities of the polyhydroxylated sterols were evaluated on prostate carcinoma LNCaP cell line.     

Prolyl endopeptidase inhibitors from the underground part of Rhodiola sachalinensis

The methanolic extract of the underground part of Rhodiola sachalinensis was found to show inhibitory activity on prolyl endopeptidase (PEP, EC. 3.4.21.26), an enzyme that plays a role in the metabolism of proline-containing neuropeptidase which is recognized to be involved in learning and memory. From the MeOH extract, five new monoterpenoids named sachalinols A (24), B (25) and C (26) and sachalinosides A (23) and B (27) were isolated, together with twenty-two known compounds, gallic acid (1), trans-p-hydroxycinnamic acid (2), p-tyrosol (3), salidroside (4), 6n-O-galloylsalidroside (5), benzyl beta-D-glucopyranoside (6), 2-phenylethyl beta-D-glucopyranoside (7), trans-cinnamyl beta-D-glucopyranoside (8), rosarin (9), rhodiocyanoside A (10), lotaustralin (11), octyl beta-D-glucopyranoside (12), 1,2,3,6-tetra-O-galloyl-beta-D-glucose (13), 1,2,3,4,6-penta-O-galloyl-beta-D-glucose (14), kaempferol (15), kaempferol 3-O-beta-D-xylofuranosyl(1-->2)-beta-D-glucopyranoside (16), kaempferol 3-O-beta-D-glucopyranosyl(1-->2)-beta-D-glucopyranoside (17), rhodionin (18), rhodiosin (19), (-)-epigallocatechin (20), 3-O-galloylepigallocatechin-(4-->8)-epigallocatechin 3-O-gallate (21) and rosiridin (22). Among these, nineteen compounds other than 3, 4 and 9 have been isolated for the first time from R. sachalinensis, and six (6, 8, 13, 16, 17, 20) are isolated from Rhodiola plants for the first time. Among them, six compounds (13, 14, 18, 19, 21, 22) showed noncompetitive inhibition against Flavobacterium PEP, with an IC50 of 0.025, 0.17, 22, 41, 0.44 and 84 microM, respectively.     

Antiplatelet and anti-HIV constituents from Euchresta formosana

Phytochemical investigation of the methanol extract of Euchresta formosana resulted in the isolation of thirty-four compounds. Compounds 1, 3-12, 15, 27, 29 and 32-24 were isolated from this species for the first time. These compounds were identified by spectral analyses and tested for antiplatelet aggregation and anti-HIV activities. Among these compounds, tectorigenin (1), 3',4',5-trihydroxyisoflavone (3), and euchretin F (19) were the most effective antiplatelet aggregation compounds; they inhibited both AA- (arachidonic acid) and collagen-induced platelet aggregation. Meanwhile, flemiphyllin (B), quercetin (13), euchretin M (23), and formosanatin C (26) inhibited HIV replication in H9 lymphocyte cells.     

Chemical constituents of Melicope ptelefolia

Phytochemical investigations on the methanolic extract of Melicope ptelefolia Champ ex Benth. resulted in the isolation of three new compounds, identified as 3beta-stigmast-5-en-3-ol butyl tridecanedioate (melicoester) (1), (2Z, 6Z, 10Z, 14Z, 18Z, 22Z, 26E)-3', 7', 11', 15', 19', 23', 27', 31'-octamethyldotriaconta-2, 6, 10, 14, 18, 22, 26, 30-octadecanoate (melicopeprenoate) (2) and p-O-geranyl-7"-acetoxy coumaric acid (3). The compounds were isolated along with twenty-one other known compounds, lupeol (4), oleanolic acid (5), kokusaginine (6) genistein (7), p-O-geranyl coumaric acid (8), 4-stigmasten-3-one (9), 3beta-hydroxystigma-5-en-7-one (10) cis-phytyl palmitate (11), dodecane, dodecan-1-ol, ceryl alcohol, hentriacontanoic acid, eicosane, n-amyl alcohol, caprylic alcohol, octatriacontane, nonatriacontane, hexatriencontan-1-ol, methyl octacosanoate, beta-sitosterol, beta-sitosterol glucoside. Structures of all the compounds were established on the basis of MS and 1D and 2D NMR spectral data, as well as comparison with reported data.     

Quadranosides VI-XI, six new triterpene glucosides from the seeds of Combretum quadrangulare

Six new triterpene glucosides, quadranosides VI-XI (1-6), belonging to three different [ursane- (1-4), oleanane- (5) and lupane-type (6)] triterpene classes, have been isolated from a MeOH extract of the seeds of Combretum quadrangulare KURZ (Combretaceae), together with nine known compounds, rosamutin (7), 28-O-beta-D-glucopyranosyl-6beta,23-dihydroxytormentic acid (8), arjunetin (9), arjunglucoside II (10), combreglucoside (11), chebuloside II (12), vitexin (13), (+)-catechin (14) and (-)-epigallocatechin (15). The structures of these compounds were elucidated by spectroscopic analysis.     

Two novel lanostane triterpenoids from Ganoderma sinense

Two novel lanostane-type triterpenes, Ganolactone B and Ganoderiol A triacetate, were isolated from the fruiting bodies of G. sinense, together with six known compounds. The structures of the two new triterpenes were determined as 3beta,7beta- dihydroxy-11,15-dioxo-lanosta-8-en-24-->20 lactone (1) and 3beta,24,26-triacetoxy-5alpha-lanosta-7,9(11)-dien-25-ol (2), respectively, by chemical and spectroscopic means.     

A new triterpene from the plant of uncaria macrophylla

Our ongoing investigations on the stem bark of Uncaria macrophylla afforded a new ursolic triterpene, 3β,6β,19α-trihydroxy-urs-12-en-28-oic acid-24-carboxylic acid methyl ester (1), named uncariursanic acid, and three known ursolic triterpenes including 3β,6β,19α-trihydroxy-23-oxo-urs-12-en-28-oic acid (2), 3β,6β,19α-trihydroxy-urs-12-en-28-oic acid (3) and ursolic acid (4). Their structures were elucidated by extensive spectral methods, including 1D and 2D NMR and HR-ESI-MS. The cytotoxicities of the four compounds were evaluated against two cancer cell lines (MCF-7 and HepG2) by the MTT method, and only compound 4 exhibited potent activity.     

Cytotoxic lupane-, secolupane-, and oleanane-type triterpenes from Viburnum awabuki

Bioassay-guided fractionation of the methanolic extract of Viburnum awabuki afforded two new lupane triterpene derivatives; 6 beta-hydroxyl-3,20-dioxo-30 norlupane-28-oic acid (1) and 3,4-secolup-4,20-dihydroxy-3,28-dioic acid-3-oic acid methyl ester (2), along with seven known lupane and oleanane-type triterpenes (3-9). The structure of the isolated compounds was assigned using different spectroscopic techniques including 1D and 2D NMR. The 13CNMR data of compounds 5 and 9 is reported for the first time. Triterpenes 1, 2, and 7-9 showed in vitro cytotoxic activity against several tumor cell lines.     

Micranoic acids A and B: two new octanortriterpenoids from Schisandra micrantha

Two novel octanortriterpenoids, micranoic acids A (1) and B (2), along with three known compounds, kadsuric acid (3), 3beta-hydroxy-lanost-9(11),24(25)-dien-26-oic acid (4) and schizandronic acid (5), were isolated from the leaves and stems of Schisandra micrantha. The structures of 1 and 2 were determined by 1D and 2D NMR spectroscopic analysis. Micranoic acids A and B represent a new group of triterpenes in which the entire C-17 side chain has lost. This is the first report of octanortriterpenoids isolated from the family Schisandraceae.