New peroxy triterpenes from the aerial roots of Ficus microcarpa

Six new triterpenes, 3 beta-acetoxy-12 beta,13 beta-epoxy-11 alpha-hydroperoxyursane (1), 3 beta-acetoxy-11 alpha-hydroperoxy-13 alpha H-ursan-12-one (2), 3 beta-acetoxy-1 beta,11 alpha-epidioxy-12-ursene (3), (20S)-3 beta-acetoxylupan-29-oic acid (4), (20S)-3 beta-acetoxy-20-hydroperoxy-30-norlupane (5), and 3 beta-acetoxy-18 alpha-hydroperoxy-12-oleanen-11-one (6), together with 3 beta-acetoxy-12-oleanen-11-one (7), were isolated from the aerial roots of Ficus microcarpa. Compounds 1-3, 5, and 6 were characterized as new peroxytriterpenes. The structures of 3 and 6 were confirmed by X-ray crystallography, and their structures were elucidated by spectroscopic and chemical methods.     

Taraxastane-type triterpenes from the aerial roots of Ficus microcarpa

Seven new taraxastane-type triterpenes-20-taraxastene-3beta, 22alpha-diol (1), 3beta-acetoxy-20-taraxasten-22alpha-ol (2), 3beta-acetoxy-22alpha-methoxy-20-taraxastene (3), 3beta-acetoxy-20alpha,21alpha-epoxytaraxastan-22alp ha-ol (4), 3beta-acetoxy-19alpha-methoxy-20-taraxastene (5), 3beta-acetoxy-19alpha-hydroperoxy-20-taraxastene (6), 3beta-acetoxy-20alpha,21alpha-epoxytaraxastane (7)-were isolated from the aerial roots of Ficus microcarpa. Their structures were elucidated by spectroscopic and chemical methods.     

Taxanes from rooted cuttings of Taxus canadensis

A 3,11-cyclotaxane (1), a new epoxytaxane (2), an abeo-taxane (3), and 26 known taxanes were isolated in rooted cuttings of the Canadian yew (Taxus canadensis) for the first time. Their chemical structures were characterized as 1 beta,2 alpha,9 alpha-trihydroxy-10 beta-acetoxy-5 alpha-cinnamoyloxy-3,11-cyclotaxa-4(20)-en-13-one (1), 2 alpha,9 alpha,10 beta-triacetoxy-11,12-epoxy-20-hydroxytaxa-4-en-13-one (2), and 7 beta,9 alpha,10 beta,13 alpha-tetraacetoxy-11(15-->1)abeo-taxa-4(20),11-diene-5 alpha,15-diol (3). Metabolite 2 is a new taxane, metabolite 1 has been reported previously in the needles of Taxus baccata, and metabolite 3 was previously discovered as a biotransformation product but is now reported as a natural product for the first time.     

Oxygenated analogues of gorgosterol and ergosterol from the soft coral Capnella lacertiliensis

From the dichloromethane solubles of Capnella lacertiliensis five new sterols were isolated that are highly functionalized with oxygen-containing substituents: 12beta-acetoxy-7alpha-hydroxygorgosterol (1), 12beta-acetoxy-7alpha,19-dihydroxygorgosterol (2), 12beta-acetoxyergost-5-ene-3beta,23-diol (4), 12beta-acetoxyergost-5-ene-3beta,11beta,16-triol (5), and 11beta-acetoxyergost-5-ene-3beta,12beta,16-triol (6). The structures of all compounds were deduced from interpretation of their spectroscopic data, mainly 1D and 2D NMR spectra and HREIMS. Biological activities of the isolates were assessed, and all were found to be weakly antifungal. Compounds 5 and 6 were also found to have weak tyrosine kinase p56(lck)() (TK) inhibitory activity at the 200 microgram/mL level.     

Beesiosides G, H, and J-N, seven new cycloartane triterpene glycosides from Beesia calthifolia

Seven new cycloartane glycosides (1-7), beesiosides G, H, and J-N, together with beesioside I (8) and beesioside A, were isolated from the rhizomes of Beesia calthifolia, and their structures were established by spectroscopic and chemical methods. Beesiosides G, H, and J-N were assigned as 20xi(1),24xi(2)-epoxy-9,19-cyclolanostane-3beta,16beta,18,25-tetraol-3-O-beta-D-glucopyranoside (1), 20xi(1),24xi(2)-epoxy-9,19-cyclolanostane-3beta,16beta,18,25-tetraol-3-O-[beta-D-glucopyranosyl-(1-->6)]-beta-D-glucopyranoside (2), (20S,24R)-15alpha,16beta-diacetoxy-20,24-epoxy-9,19-cyclolanostane-3beta,18,25-triol-3-O-beta-D-xylopyranoside (3), (20S,24S)-16beta-acetoxy-18,24;20,24-diepoxy-9,19-cyclanostane-3beta,15beta,25-triol-3-O-beta-D-xylopyranoside (4), (20S,24S)-16beta-acetoxy-18,24;20,24-diepoxy-9,19-cyclanostane-3beta,25-diol-3-O-beta-D-xylopyranoside (5), 20xi(1),24xi(2)-epoxy-15alpha-acetoxy-9,19-cyclolanostane-3beta,16beta,25-triol-3-O-beta-D-xylopyranoside (6), and 20xi(1),24xi(2)-epoxy-9,19-cyclolanostane-3beta,12alpha,15alpha,16beta,25-pentaol-3-O-beta-D-xylopyranoside (7), respectively.     

Beesiosides A-F, six new cycloartane triterpene glycosides from Beesia calthaefolia.

Six new cycloartane triterpene glycosides (1-6), beesiosides A-F, were isolated from whole plants of Beesia calthaefolia, and their structures were elucidated on the basis of extensive NMR experiments and chemical methods. Beesiosides A-F were assigned as (20S,24R)-epoxy-9,19-cyclolanostane-3beta,16beta,18,25-tetraol-3-O-beta-D-xylopyranoside (1), (20S,24R)-epoxy-9,19-cyclolanostane-3beta,12beta,16beta,18,25-pentaol-3-O-beta-D-xylopyranoside (2), (20S,24R)-epoxy-9,19-cyclolanostane-3beta,12alpha,16beta,18,25-pentaol-3-O-beta-D-xylopyranoside (3), (20S,24R)-16beta-acetoxy-20,24-epoxy-9,19-cyclolanostane-3beta,12alpha,18,25-tetraol-3-O-beta-D-xylopyranoside (4), (20S,24R)-epoxy-9,19-cyclolanostane-3beta,15alpha,16beta,18,25-pentaol-3-O-beta-D-xylopyranoside (5), and (20S,24R)-16beta-acetoxy-20,24-epoxy-9,19-cyclolanostane-3beta,12beta,25-triol-3-O-beta-D-xylopyranoside (6), respectively.     

Insect antifeedant activity of three new tetranortriterpenoids from Trichilia pallida

Three new tetranortriterpenoids, methyl 6-hydroxy-11 beta-acetoxy-12 alpha-(2-methylpropanoyloxy)-3,7-dioxo-14 beta,15 beta-epoxy-1,5-meliacadien-29-oate (3), methyl 6,11 beta-dihydroxy-12 alpha-(2-methylpropanoyloxy)-3,7-dioxo-14 beta,15 beta-epoxy-1,5-meliacadien-29-oate (4), and methyl 6-hydroxy-11 beta-acetoxy-12 alpha-(2-methylbutanoyloxy)-3,7-dioxo-14 beta,15 beta-epoxy-1,5-meliacadien-29-oate (5), have been isolated from the roots of Trichilia pallida. The related compounds hirtin (1) and deacetylhirtin (2) were also obtained. Compound 4 had the greatest antifeedant activity of 1-5 when tested against larvae of four species of Lepidoptera.     

Highly hydroxylated triterpenes from Salvia kronenburgii

The three new triterpenes (1-3) and five known triterpenes and a sterol were isolated from the acetone extract of a Turkish collection of Salvia kronenburgii. The structures of the new triterpenes were established as 1beta,2alpha-dihydroxy-3beta-acetoxy-11-oxours-12-ene (1), 2alpha,20beta-dihydroxy-3beta-acetoxyurs-9(11),12-diene (2), and 1beta,2alpha-dihydroxy-3beta-acetoxyurs-9(11),12-diene (3) on the basis of spectral analyses, including 1D and 2D NMR and mass spectroscopy. It is probable that compounds 2 and 3 are artifacts from dehydration of the corresponding allylic alcohols. 1beta,2alpha,3beta,11alpha-Tetrahydroxyurs-12-ene (5), the most abundant compound in the extract, was found to be highly cytotoxic to renal, non-small cell lung, and breast cancer cell lines.     

Longipinane derivatives from Stevia connata

The hexane extracts of the roots of Stevia connata afforded three new longipinene derivatives, longipinane-7beta,8alpha, 9alpha-triol-1-one 7-angelate-8-methylbutyrate (1), longipin-2-ene-7beta,8alpha,9alpha-triol-1-one 8,9-diangelate (6), and longipin-2-ene-7beta,8alpha,9alpha-triol-1-one 8-angelate-9-methylbutyrate (8), together with the known longipinane-7beta,8alpha,9alpha-triol-1-one 8,9-diangelate (2), longipinane-7beta,8alpha,9alpha-triol-1-one 7,9-diangelate (3), longipinane-7beta,8alpha,9alpha-triol-1-one 7,8-diangelate (4), longipin-2-ene-7beta,8alpha,9alpha-triol-1-one 7,8-diangelate (5), longipin-2-ene-7beta,8alpha,9alpha-triol-1-one 7-angelate-8-methylbutyrate (12), and stigmasterol. The structures of the new compounds were determined by chemical transformations and spectral methods including 2D NMR measurements. Spontaneous intramolecular transesterifications starting from the 8-angelate-9-methylbutyrate 8 provided an equilibrated mixture of the 7-angelate-9-methylbutyrate 10, the 7-angelate-8-methylbutyrate 12 and the starting material when stored in MeOH-H(2)O solution, while the 8,9-diangelate 6 only provided a binary mixture of the 7, 9-diangelate 7 and the starting material under the same conditions. The structures of 6-8, 10, and 12 and those of the nonisolable reaction intermediates 9, 11, and 14 were further evaluated by AM1 semiempirical calculations.     

Jatrophane diterpenoids from Euphorbia mongolica as modulators of the multidrug resistance of L5128 mouse lymphoma cells

The dried aerial parts of Euphorbia mongolica afforded three new acylated polyhydroxy diterpenoids based on the jatrophane framework. The structures were established by means of a combination of 1D and 2D NMR techniques and mass spectrometry as (2S,3S,4R,5R,7S,8R,13S,15R)-5alpha,7beta,8alpha-triacetoxy-3beta-benzoyloxy-15beta-hydroxyjatropha-6(17),11E-diene-9,14-dione (1), (2S,3S,4R,5R,7S,8S,9S13S,15R)-5alpha,7beta,8alpha,9alpha,15beta-pentaacetoxy-3beta-benzoyloxyjatropha-6(17),11E-dien-14-one (2), and (2S,3S,4R,5R,7S,8S,9S13S,15R)-3beta,7beta,8alpha,9alpha,15beta-pentaacetoxy-5alpha-benzoyloxyjatropha-6(17),11E-dien-14-one (3). When the isolates were assayed for multidrug resistance-reversing activity in a rhodamine 123 exclusion test using L5178 mouse lymphoma cells, all compounds demonstrated a concentration-dependent effect in inhibiting the efflux pump activity of these tumor cells in the range 11.2-112 microM.     

Five new insecticidal sesquiterpenoids from Celastrus angulatus

Five new sesquiterpene polyol esters were isolated from the root bark of Celastrus angulatus by bioassay-guided fractionation. Their structures were determined by spectral data interpretation as 1alpha,2alpha,6beta,8beta,13-pentaacetoxy-9beta-benzoyloxy-4beta-hydroxy-beta-dihydroagarofuran (1), 1alpha,2alpha,6beta-triacetoxy-8alpha-(beta-furancarbonyloxy)-9beta-benzoyloxy-13-isobutanoyloxy-4beta-hydroxy-beta-dihydroagarofuran (2), 1alpha,2alpha,6beta-triacetoxy-8beta-isobutanoyloxy-9beta-(beta-furancarbonyloxy)-13-(alpha-methyl)butanoyloxy-4beta-hydroxy-beta-dihydroagarofuran (3), 1alpha,2alpha,6beta-triacetoxy-8alpha,13-diisobutanoyloxy-9beta-benzoyloxy-4beta-hydroxy-beta-dihydroagarofuran (4), and 1alpha,2alpha,6beta-triacetoxy-8alpha-isobutanoyloxy-9beta-benzoyloxy-13-(alpha-methyl)butanoyloxy-4beta-hydroxy-beta-dihydroagarofuran (5). Compounds 1-5 exhibited insecticidal activity against the larval of Mythimna separata.     

Triterpene glycosides from Cimicifuga racemosa

Eight new triterpene glycosides named cimiracemosides A-H, respectively, and eight known triterpene glycosides were isolated from the rhizome extracts of black cohosh (Cimicifuga racemosa). The new compounds were determined by spectral data to be 21-hydroxycimigenol-3-O-alpha-L-arabinopyranoside (1), 21-hydroxycimigenol-3-O-beta-D-xylopyranoside (2), cimigenol-3-O-alpha-L-arabinopyranoside (3), 12beta-acetoxycimigenol-3-O-alpha-L-arabinopyranoside (4), 24-acetylisodahurinol-3-O-beta-D-xylopyranoside (5), 20(S),22(R), 23(S),24(R)-16beta:23;22:25-diepoxy-12beta-acetoxy-3be ta,23, 24-trihydroxy-9,19-cycloanost-7-ene-3-O-beta-D-xylopyranoside (6), 20(S),22(R),23(S),24(R)-16beta:23;22:25-diepoxy-12beta -acetoxy-3beta, 23,24-trihydroxy-9,19-cycloanost-7-en-3-O-alpha-L-arabinopyrano side (7), and 20(S),22(R),23(S), 24(R)-16beta:23;22:25-diepoxy-12beta-acetoxy-3beta,23, 24-trihydroxy-9,19-cycloanostane-3-O-beta-D-xylopyranoside (8).     

短柄小连翘中的木脂素类化学成分研究

目的:对短柄小连翘Hypericum petiolulatum的化学成分进行系统的研究.方法:采用硅胶、大孔吸附树脂、Sephadex LH-20柱色谱和制备型高效液相色谱方法进行分离;应用NMR和MS等波谱学方法鉴定化合物的结构.结果:从短柄小连翘乙醇提取物中分离得到9个木脂素类成分,分别鉴定为(-)-(2R,3R)-1-O-feruloy1-8,8'-bisdihydrosiringenin(1),(-)-secoisolariciresinol 4-O-β-D-glucopyranoside(2),isolaricire-sinol-β-4'-O-β-D-glucopy-ranoside(3),5-methoxy-9β-xylopyranosyl-(+)-isolariciresinol(4),(+)-lyoniresinol-2α-O-β-D-xylopyranoside(5),5-methoxy-9-β-xylopyranosyl一(一)-isolariciresinol(6),isolariciresinol 6a-O-β-D-glucoside(7),(+)-lyoniresinol 3α-O-β-D-xylopyranoside(8)和7-methoxy-5-benzofuranpropanol 4'-O-β-D-glucopyranoside(9).结论:化合物1为一新化合物,其余化合物均为首次从该属植物中分离得到.     

Taxane diterpenoids from the stem bark of Taxus mairei

Three new 11(15-->1)-abeo-taxanes, taxumairols U-W (1-3), have been isolated from extracts of the stem bark of Formosan Taxus mairei. The structures of 1-3 were identified as 5alpha,7beta,9alpha,13alpha,20-pentaacetoxy-2alpha,10beta,15-trihydroxy-11(15-->1)-abeo-taxene, 5alpha,7beta,9alpha,20-tetraacetoxy-2alpha,10beta,13alpha,15-tetrahydroxy-11(15-->1)-abeo-taxene, and 2alpha,4alpha,7beta,10beta-tetraacetoxy-5beta,20-epoxy-9alpha,13alpha,15-trihydroxy-11(15-->1)-abeo-taxene, respectively, on the basis of 2D NMR techniques including COSY, HSQC, HMBC, and NOESY experiments as well as chemical reactions of compounds 1-3 to give 4 (5alpha,7beta,9alpha,10beta,13alpha,20-hexaacetoxy-2alpha,15-dihydroxy-11(15-->1)-abeo-taxene) and 5 (4alpha,7beta,10beta-triacetoxy-9alpha,13alpha-dibenzoxy-5beta,20-epoxy-2alpha,15-dihydroxy-11(15-->1)-abeo-taxene), which are also novel taxane derivatives. Taxumairols U (1) and V (2) exhibited significant cytotoxicities against human hepatoma tumor cells, while taxumairol W (3) was inactive.     

东北红豆杉心材化学成分的研究

目的:研究东北红豆杉心材的化学成分。方法:采用硅胶柱色谱、制备薄层色谱和制备型高效液相色谱等手段对化学成分进行分离和纯化,用现代核磁技术对化合物进行结构鉴定。结果:从东北红豆杉心材分离得到10个化合物,分别鉴定为taxin ine(1),taxusin(2),-βsitosterol(3),1-βhydroxybaccatin I(4),2,α5,α10β-triace-toxy-14β-(2-′m ethyl)butanoyloxy-4(20),11-taxad iene(5),2,α5,α10-βtriacetoxy-14-β(2-′m ethyl-3-′hydroxy-butanoy-loxy)-4(20),11-taxad iene(yunnanxane)(6),9,α10,β13α-triacetoxy-5-αc innamoyltaxa-4(20),11-d iene(7),2-deace-toxytaxin ine J(8),taxezop id ine G(9),2,α7,β9,α10,β13-αpentaacetoxyl-taxa-4(20),11-d ien-5-ol(5-dec innamoyltaxi-n ine J)(10)。结论:化合物4,6,10是首次从该植物中分离得到。     

Antimycobacterial activity of phorbol esters from the fruits of Sapium indicum

Three new phorbol esters, 12-(2-N-methylaminobenzoyl)-4beta,5,20-trideoxyphorbol-13-acetate (1), 12-(2-N-methylaminobenzoyl)-4alpha,5,20-trideoxyphorbol-13-acetate (2), and 12-(2-N-methylaminobenzoyl)-4alpha, 20-dideoxy-5-hydroxyphorbol-13-acetate (6), together with six known compounds (3-5 and 7-9), were isolated from the fruits of Sapium indicum. The chemical structures of 1, 2, and 6 were elucidated by analysis of their spectroscopic data. Compounds 1-3, 5, and 7-9 exhibited antimycobacterial activity with minimum inhibitory concentrations (MIC) between 3.12 and 200 microg/mL, but compounds 4 and 6 were inactive (MIC >200 microg/mL).     

New taxanes from the needles of Taxus canadensis

Ten new taxanes were isolated from the methanol extract of the needles of the Canadian yew, Taxus canadensis. On the basis of their spectral analysis, their structures were established as 9alpha-hydroxy-2alpha,7alpha,10beta-triacetoxy-5alpha-cinnamoyloxy-3,11-cyclotaxa-4(20)-en-13-one (1), 9alpha,10beta-diacetoxy-5alpha-cinnamoyloxy-3,11-cyclotaxa-4(20)-en-13-one (2), 9alpha,20-dihydroxy-2alpha,10beta,13alpha-triacetoxytaxa-4(5),11(12)-diene (3), 2alpha,9alpha,10beta-triacetoxy-20-cinnamoyloxy-11,12-epoxytaxa-4-en-13-one (4), 9alpha-hydroxy-2alpha,10beta,13alpha-triacetoxy-5alpha-(3'-methylamino-3'-phenyl)-propionyloxytaxa-4(20),11-diene (5), 2alpha,10beta-diacetoxy-5alpha,9alpha-dihydroxytaxa-4(20),11-dien-13-one (6), 2alpha,9alpha-diacetoxy-5alpha,10beta-dihydroxytaxa-4(20),11-dien-13-one (7), 5alpha,9alpha-dihydroxy-2alpha,10beta,13alpha-triacetoxytaxa-4(20),11-diene (8), 5alpha,10beta-dihydroxy-2alpha,9alpha,13alpha-triacetoxytaxa-4(20),11-diene (9), and 7beta,11beta-dihydroxy-2alpha,9alpha,10beta,13-tetraacetoxy-5alpha-cinnamoyloxytaxa-4(20),12-diene (10). Taxane 1 is the first example of a 3,11-cyclotaxane with a 7-epi-alpha-oxygenated group. Taxane 4 is the first taxane with a C-11,12-epoxide ring as well as a C-4(5)-endo-double bond. Taxanes with a 12(13) double bond as in 10 instead of the usual 11(12) double bond have been found so far only in the needles, stem, and seeds of the Japanese yew.     

Cucurbitane-type triterpenoids from the stems of momordica charantia

Four new cucurbitane-type triterpenes, cucurbita-5,23(E)-diene-3beta,7beta,25-triol (1), 3beta-acetoxy-7beta-methoxycucurbita-5,23(E)-dien-25-ol (2), cucurbita-5(10),6,23(E)-triene-3beta,25-diol (5), and cucurbita-5,24-diene-3,7,23-trione (6), together with four known triterpenes, 3beta,25-dihydroxy-7beta-methoxycucurbita-5,23(E)-diene (3), 3beta-hydroxy-7beta,25-dimethoxycucurbita-5,23(E)-diene (4), 3beta,7beta,25-trihydroxycucurbita-5,23(E)-dien-19-al (7), and 25-methoxy-3beta,7beta-dihydroxycucurbita-5,23(E)-dien-19-al (8), were isolated from the methyl alcohol extract of the stems of Momordica charantia. The structures of the new compounds were elucidated by spectroscopic methods.     

Chiral decalins: preparation from oleanolic acid and application in the synthesis of (-)-9-epi-ambrox

A novel and versatile process was developed to prepare the trans-decalins Delta9(11)-3beta-acetoxysclareolide (2) and Delta9(11)-3beta-acetoxy-8-epi-sclareolide (3), respectively, with 4a-methoxycarbonyl-2,7,7-trimethyl-1-oxo-cis-decalin-2-ene (4) and its C-3 hydroxyl derivative 5 from oleanolic acid (3beta-hydroxyolean-12-en-28-oic acid, 1). Three key steps were (a) introduction of the AcO-12 group and the C-9,C-11 double bond at ring C of methyl 3beta-acetoxyolean-12-en-28-oate (8) to afford the diene, methyl 3,12-diacetoxyolean-9(11),12-dien-28-oate (11); (b) photolytic cleavage of the C-8,C-14 bond in the diene to give an acetoxy-substituted triene 14; and (c) oxidative cleavage of the triene or its hydrolyzed alpha,beta-unsaturated ketone product with m-CPBA/TsOH to give the cis- and trans-decalins 2-5. Delata9(11)-3beta-Acetoxysclareolide (2) was stereospecifically reduced to give 3beta-acetoxy-9-epi-sclareolide (23), from which (-)-9-epi-ambrox (7) was synthesized.     

Sesquiterpenoids from Tithonia diversifolia with potential cancer chemopreventive activity

Activity-guided fractionation of an ethyl acetate extract of the aerial parts of Tithonia diversifolia, using an antiproliferation bioassay performed with human colon cancer (Col2) cells, led to the isolation of three new sesquiterpenoids, 2alpha-hydroxytirotundin (1), tithofolinolide (2), and 3alpha-acetoxydiversifolol (3), along with eight known sesquiterpene lactones, 3beta-acetoxy-8beta-isobutyryloxyreynosin (4), tagitinin C (5), 1beta,2alpha-epoxytagitinin C (6), 4alpha,10alpha-dihydroxy-3-oxo-8beta-isobutyryloxyguaia-11(13)-en-12,6alpha-olide (7), 3alpha-acetoxy-4alpha-hydroxy-11(13)-eudesmen-12-oic acid methyl ester, 17,20-dihydroxygeranylnerol, tagitinin A, and tirotundin. These isolates were evaluated for their potential as cancer chemopreventive agents, by measuring antiproliferative activity in Col2 cells and induction of cellular differentiation in human promyelocytic leukemia (HL-60) cells. Selected compounds were then investigated for their ability to inhibit 7,12-dimethylbenz[a]anthracene-induced preneoplastic lesions in a mouse mammary organ culture assay. Among these isolates, 5 and 6 showed significant antiproliferative activity, 2, 4, and 7 induced HL-60 cellular differentiation, and 4 significantly inhibited (63.0% at 10 microg/mL) lesion formation in the mouse mammary organ culture assay. The chemical structures of 1-3 were elucidated by spectroscopic analysis. The absolute configurations of 1 and 2 were determined by Mosher ester methodology.