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.     

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.     

Secondary metabolites from the roots of Astragalus trojanus

Six novel cycloartane-type glycosides were isolated from the roots of Astragalus trojanus. Two of these, compounds 1 and 2, have (20R, 24S)-epoxy-3beta,6alpha,16beta,25-tetrahydroxycycloartane as the aglycon, while compounds 3-6 possess 3beta,6alpha,16beta,(24S), 25-pentahydroxycycloartane as the aglycon. The saccharide moieties linked to the C-3, C-6, and C-24 or C-25 positions of the aglycons in 1-6 contained either xylopyranose, glucopyranose, rhamnopyranose, or arabinopyranose units. Structure elucidation of compounds 1-6 was accomplished through the extensive use of 1D and 2D NMR techniques. In addition, a new oleanene glycoside (7) and a new tryptophan derivative (8) were also isolated and characterized.     

ent-Kaurane and beyerane diterpenoids from Excoecaria agallocha

The roots of Excoecaria agallocha yielded four new diterpenoids, ent-3 beta,20-epoxy-3 alpha,6 alpha-dihydroxykaur-16-ene (agallochin F) (1), 3beta,20-epoxy-3 alpha-hydroxybeyer-15-ene (agallochin G) (2), 3 beta,20:15R,16S-diepoxy-3 alpha-beyeranol (agallochin H) (3), and 3 beta,20-epoxy-3 alpha,6 alpha-dihydroxy-18-nor-beyer-15-ene (agallochin I) (4), along with three known derivatives, 2-acetoxy-1,15-beyeradiene-3,12-dione (5), 2-hydroxy-1,15-beyeradiene-3,12-dione (6), and ent-kauran-16 beta-ol-3-one. The structures of 1-4 were determined by spectroscopic (NMR and MS) data interpretation.     

Cycloartane triterpenoids from Astragalus bicuspis

Three new cycloartane glycosides have been isolated from Astragalus bicuspis. They were identified as 6alpha-hydroxy-3-O-beta-xylopyranosyloxy-24,25,26,27-tetranor-9,19-cyclolanosta-16,23-lactone (1), 6alpha-hydroxy-23-methoxy-16beta,23(R)-epoxy-24,25,26,27-tetranor-9,19-cyclolanosta-3-O-beta-xyloside (2), and 23(R),24(S),25(R),26(S)-16beta/23,23/26,24/25-triepoxy-6alpha,26-dihydroxy-9,19-cyclolanosta-3-O-beta-xyloside (3), on the basis of their spectroscopic data. Two known cycloartane derivatives, 4 and 5, were also obtained from this plant. Compounds 2-5 were tested for leishmanicidal activity against Leishmania major promastigotes and for cytotoxicity against 3T3 cancer cells.     

Phrygiasterol, a cytotoxic cyclopropane-containing polyhydroxysteroid, and related compounds from the pacific starfish Hippasteria phrygiana

The new cyclopropane-containing steroid phrygiasterol (1) and steroid glycoside phrygioside B (2), along with previously known borealoside C (2a) and (20R,24S)-5alpha-cholesta-3beta,6alpha,8,15alpha,24-pentaol (3), have been isolated from the Pacific starfish Hippasteria phrygiana. On the basis of spectroscopic analyses, using 1D and 2D NMR techniques and some chemical transformations, the structures of 1 and 2 have been established as (20R,24R,25R)-24,26-cyclo-5alpha-cholesta-3beta,6alpha,8,15alpha,16beta,27-hexaol (1) and the sodium salt of (20R,24S)-24-O-(3-O-methyl-4-O-sulfate-beta-d-xylopyranosyl)-5alpha-cholesta-3beta,6alpha,8,15alpha,24-pentaol (2), respectively. Compound 1 inhibited the growth of Ehrlich carcinoma cells with an IC(50) of 50 microg/mL, whereas 2 induced apoptosis of the same cells (EC(50)=70 microg/mL) and inhibited Ca(2+) influx into mouse spleenocytes (EC(50)=20microg/mL).     

Withanolides from Vassobia lorentzii

Eight new withanolides were isolated from the aerial parts of Vassobia lorentzii and characterized by spectroscopic methods and with the aid of molecular modeling. The compounds were identified as (17S,20R,22R)-5beta,6beta:18,20-diepoxy-18-hydro xy-1-oxowitha-2,5, 24-trienolide (1); (17S,20R,22R)-18,20-epoxy-4beta, 18-dihydroxy-1-oxowitha-2,5,24-trienolide (2); (17S,18R,20R, 22R)-4beta-hydroxy-18,20-epoxy-18-methoxy-1-oxowitha-2,5, 24-trienolide (3); (17S,18S,20R,22R)-4beta-hydroxy-18, 20-epoxy-18-methoxy-1-oxowitha-2,5,24-trienolide (4); (17S,20R, 22R)-4beta-hydroxy-18,20-epoxy-1,18-dioxowitha-2,5,24-tri enolide (5); (17S,18R,20R,22R)-18,20-epoxy-18-methoxy-1,4-dioxowitha++ +-2,5, 24-trienolide (6); (17S,18S,20R,22R)-18,20-epoxy-18-methoxy-1, 4-dioxowitha-2,5,24-trienolide (7); and (17S,20R,22R)-5beta, 6beta-epoxy-4beta,18,20-trihydroxy-1-oxowitha-2,24-die nolide (8). Compounds 1 and 2 were obtained as epimeric mixtures at C-18.     

Eucosterol-type nortriterpenoids from Merwilla natalensis

The bulbs of Merwilla natalensis have yielded two known homoisoflavanones, the known spirocyclic homoisoflavanone, scillascillin, four known nortriterpenoids, and the new nortriterpenoid, (22R,23S)-17alpha,23-epoxy-22,29-dihydroxy-27-nor-lanost-8-en-3,24-dione (1), bisnortriterpenoid, (22R,23S)-17alpha,23-epoxy-3beta,22,24xi-trihydroxy-27,28-bisnor-lanost-8-ene (2), and trisnortriterpenoid, (23S)-17alpha,23-epoxy-3beta,24xi-dihydroxy-27,28,29-trisnor-lanost-8-ene (3). The structures of 1-3 were determined by spectroscopic methods.     

Antitubercular activity of triterpenoids from Lippia turbinata

Assay-guided fractionation of the antitubercular MeOH-CH(2)Cl(2) extract obtained from Lippia turbinata led to the isolation of four novel triterpenoids-3beta,25-epoxy-3alpha,21alpha-dihydroxy-22beta-(3-methylbut-2-en-1-oyloxy)olean-12-ene-28-oic acid (1); 3beta,25-epoxy-3alpha,21alpha-dihydroxy-22beta-angeloyloxyolean-12-ene-28-oic acid (2); 3beta,25-epoxy-3alpha,21alpha-dihydroxy-22beta-tigloyloxyolean-12-ene-28-oic acid (3); and 3beta,25-epoxy-3alpha-hydroxy-22beta-(2-methylbutan-1-oyloxy)olean-12-ene-28-oic acid (4)-together with the known triterpenoids lantanilic acid (5), camaric acid (6), lantanolic acid (7), and rehmannic acid (8). The MIC values of 1-8 for growth inhibition of Mycobacterium tuberculosis were determined in the radiorespirometric BACTEC system.     

Microbial transformation of 20(S)-protopanaxatriol-type saponins by Absidia coerulea

Three 20(S)-protopanaxatriol-type saponins, ginsenoside-Rg1 (1), notoginsenoside-R1 (2), and ginsenoside-Re (3), were transformed by the fungus Absidia coerulea (AS 3.3389). Compound 1 was converted into five metabolites, ginsenoside-Rh4 (4), 3beta,2beta,25-trihydroxydammar-(E)-20(22)-ene-6-O-beta-D-glucopyranoside (5), 20(S)-ginsenoside-Rh1 (6), 20(R)-ginsenoside-Rh1 (7), and a mixture of 25-hydroxy-20(S)-ginsenoside-Rh1 and its C-20(R) epimer (8). Compound 2 was converted into 10 metabolites, 20(S)-notoginsenoside-R2 (9), 20(R)-notoginsenoside-R2 (10), 3beta,12beta,25-trihydroxydammar-(E)-20(22)-ene-6-O-beta-D-xylopyranosyl-(1-->2)-beta-D-glucopyranoside (11), 3beta,12beta-dihydroxydammar-(E)-20(22),24-diene-6-O-beta-D-xylopyranosyl-(1-->2)-beta-D-glucopyranoside (12), 3beta,12beta,20,25-tetrahydroxydammaran-6-O-beta-D-xylopyranosyl-(1-->2)-beta-D-glucopyranoside (13), and compounds 4-8. Compound 3 was metabolized to 20(S)-ginsenoside-Rg2 (14), 20(R)-ginsenoside-Rg2 (15), 3beta,12beta,25-trihydroxydammar-(E)-20(22)-ene-6-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranoside (16), 3beta,12beta-dihydroxydammar-(E)-20(22),24-diene-6-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranoside (17), 3beta,12beta,20,25-tetrahydroxydammaran-6-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranoside (18), and compounds 4-8. The structures of five new metabolites, 10-13 and 16, were established by spectroscopic methods.     

杂交贝母生物碱成分的研究

目的 :对杂交贝母进行化学成分研究。方法 :采用IR ,¹H NMR ,¹³ C-NMR ,2D-NMR ,MS及与对照品和文献对照等方法鉴定结构。结果 :分离并鉴定了 7个化合物 :湖贝乙素 (hupehenirine ,ZF1) ;湖贝嗪 (hupehenizine ,ZF2 ) ;浙贝乙素 (peiminine ,verticinone ,ZF3) ;湖贝甲素 (hupehenine ,ZF4 )、异浙贝甲素 (isoverticinone ,ZF5 )、浙贝甲素(peimine ,verticine ,ZF6 )、湖贝甲素苷 (hupeheninoside,ZF7) ;结论 :化合物 1～ 7均为首次从杂交贝母中得到。     

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).     

Acetals of three new cycloartane-type saponins from Egyptian collections of Astragalus tomentosus

Three new cycloartane-type saponin ethyl acetals, deacetyltomentoside I (2), tomentoside III (3), and tomentoside IV (4), were isolated along with the known acetal tomentoside I (1) from the aerial parts of Astragalus tomentosus of Egyptian origin. The saponins from which the acetals are most probably derived are also new compounds. The structures of the acetals were established as 6alpha-hydroxy-23alpha-ethoxy-16beta,23(R)-epoxy-24,25,26,27-tetranor-9,19-cyclolanosta-3-O-beta-d-xyloside (2), 6alpha-acetoxy-23alpha-ethoxy-16beta,23(R)-epoxy-24,25,26,27-tetranor-9,19-cyclolanosta-3-O-[beta-d-(4'-trans-2-butenoyl)]xyloside (3), and 6alpha-acetoxy-23alpha-ethoxy-16beta,23(R)-epoxy-24,25,26,27-tetranor-9,19-cyclolanosta-3-O-[beta-d-glucopyranosyl(1 --> 2)]-beta-d-xyloside (4), by detailed spectroscopic and chemical studies.     

Actaeaepoxide 3-O-beta-D-xylopyranoside, a new cycloartane glycoside from the rhizomes of Actaea racemosa (Cimicifuga racemosa)

A new cycloartane glycoside (1) was obtained from a minor triterpene fraction of the rhizome extract of Actaea racemosa (synonym: Cimicifuga racemosa) along with a known compound, cimigenol 3-O-beta-D-xylopyranoside. The structure of 1 was elucidated as 20(S),22(R),23(R),24(S)-12beta-acetoxy-16beta:23,23alpha:24-diepoxy-3beta,22beta,25-trihydroxy-9,19-cyclolanost-7-ene 3-O-beta-D-xylopyranoside (actaeaepoxide 3-O-beta-D-xylopyranoside) on the basis of spectral and chemical evidence.     

ent-Kaurane diterpenoids from Isodon japonicus

Five ent-kaurane diterpenoids, 6beta,7beta,14beta-trihydroxy-1alpha,19-diacetoxy-7alpha,20-epoxy- ent-kaur-16-en-15-one (1), 1alpha,6beta,7beta-trihydroxy-11alpha,19-diacetoxy-7alpha,20-epoxy-ent-kaur-16-en-15-one (2), 6-hydroxy-1alpha,19-diacetoxy-6,7-seco-ent-kaur-16-en-15-one-7,20-olide (3), 19-hydroxy-1alpha,6-diacetoxy-6,7-seco- ent-kaur-16-en-15-one-7,20-olide (4), and 6-aldehyde-1alpha,19-diacetoxy-6,7-seco- ent-kaur-16-en-15-one-7,20-olide (5), along with 10 known ent-kaurane diterpenoids, pseurata C (6), longikaurin C (7), effusanin C (8), longikaurin B (9), longikaurin D (10), effusanin D (11), excisanin B (12), lasiokaurin (13), megathyrin A (14), and loxothyrin A (15), were isolated from the aerial parts of Isodon japonicus. Their structures were determined on the basis of spectroscopic (1D-, 2D-NMR and MS) and chemical evidence. The isolates were evaluated for their inhibitory effects on LPS-induced production of nitric oxide in murine macrophage RAW264.7 cells.     

Novel diterpenoids and diterpenoid glycosides from Siegesbeckia orientalis

Eight new ent-pimarane diterpenoids and diterpenoid glycosides, namely, ent-12alpha,16-epoxy-2beta,15alpha,19-trihydroxypimar-8-ene (1), ent-12alpha,16-epoxy-2beta,15alpha,19-trihydroxypimar-8(14)-ene (2), ent-2alpha,15,16,19-tetrahydroxypimar-8(14)-ene, ent-15-oxo-2beta,16,19-trihydroxypimar-8(14)-ene, ent-2-oxo-15,16-dihydroxypimar-8(14)-en-16-O-beta-glucopyranoside, ent-2-oxo-15,16,19-trihydroxypimar-8(14)-ene, ent-2-oxo-3beta,15,16-trihydroxypimar-8(14)-en-3-O-beta-glucopyranoside, and ent-2beta,15,16,19-tetrahydroxypimar-8(14)-en-19-O-beta-glucopyranoside, together with seven known diterpenes were isolated from Siegesbeckia orientalis. Compounds 1 and 2 are novel ent-pimarane diterpenoids with an unprecedented 12alpha,16-epoxy group. Their structures were established by spectral methods, especially 1D and 2D NMR spectral methods.     

Four new dammarane saponins from Zizyphus lotus

Five dammarane-type saponins were isolated by means of centrifugal partition chromatography from the leaves of Zizyphus lotus. Their structures were elucidated using a combination of 1D and 2D 1H and 13C NMR spectra and mass spectroscopy. One of these glycosides is the known jujuboside B (5). Three are new jujubogenin glycosides, identified as 3-O-alpha-L-rhamnopyranosyl-(1-->6)-beta-D-glucopyranosyljujubogenin-20-O-(2,3,4-O-triacetyl)-alpha-L-rhamnopyranoside (1), 3-O-alpha-L-rhamnopyranosyl-(1-->6)-beta-D-glucopyranosyljujubogenin-20-O-alpha-L-rhamnopyranoside (2), and 3-O-alpha-L-rhamnopyranosyl-(1-->2)-[(4-sulfo)-beta-D-glucopyranosyl-(1-->3)]-alpha-L-arabinopyranosyljujubogenin (3). The last is a new sulfated derivative of jujubasaponine IV, identified as 3-O-alpha-L-rhamnopyranosyl-(1-->2)-[(4-sulfo)-beta-D-glucopyranosyl-(1-->3)]-beta-D-galactopyranosyl-(20R,22R)-16beta,22:16alpha,30-diepoxydammar-24-ene-3beta,20-diol (4).     

Cucurbitane-type triterpenoids from the fruit of Momordica charantia

The structures of three new cucurbitane-type triterpenoids isolated from the methanol extract of the fruit of Japanese Momordica charantia were established as (19R,23E)-5beta,19-epoxy-19-methoxycucurbita-6,23,25-trien-3beta-ol (1), (23E)-3beta-hydroxy-7beta-methoxycucurbita-5,23,25-trien-19-al (2), and (23E)-3beta-hydroxy-7beta,25-dimethoxycucurbita-5,23-dien-19-al (3) on the basis of spectroscopic methods. These compounds were accompanied by the known (19R,23E)-5beta,19-epoxy-19,25-dimethoxycucurbita-6,23-dien-3beta-ol (4) and (19R,23E)-5beta,19-epoxy-19-methoxycucurbita-6,23-diene-3beta,25-diol (5). This is the first report of the isolation of tetracyclic triterpenoids possessing a delta23,25-conjugated diene system, viz., 1 and 2, from a natural source.     

Natural products inhibiting Candida albicans secreted aspartic proteases from Lycopodium cernuum

Activity-guided fractionation of an ethanol extract of Lycopodium cernuum for Candida albicans secreted aspartic proteases (SAP) inhibition resulted in the identification of six new (1-6) and four known (7-10) serratene triterpenes, along with the known apigenin-4'-O-(2' ',6' '-di-O-p-coumaroyl)-beta-D-glucopyranoside (11). On the basis of spectroscopic analysis, the structures of 1-10 were established as 3beta,14alpha,15alpha,21beta,29-pentahydroxyserratane-24-oic acid (lycernuic acid C, 1), 3beta,14alpha,15alpha,21beta-tetrahydroxyserratane-24-oic acid (lycernuic acid D, 2), 3beta,14beta,21beta-trihydroxyserratane-24-oic acid (lycernuic acid E, 3), 3beta,21beta,29-trihydroxy-16-oxoserrat-14-en-24-methyl ester (lycernuic ketone A, 4), 3alpha,21beta,29-trihydroxy-16-oxoserrat-14-en-24-methyl ester (lycernuic ketone B, 5), 3alpha,21beta,24-trihydroxyserrat-14-en-16-one (lycernuic ketone C, 6), 3beta,21beta-dihydroxyserrat-14-en-24-oic acid (lycernuic acid A, 7), 3beta,21beta,29-trihydroxyserrat-14-en-24-oic acid (lycernuic acid B, 8), serrat-14-en-3beta,21beta-diol (9), and serrat-14-en-3beta,21alpha-diol (10). The 13C NMR data for the known compounds 7 and 8 are reported for the first time. Compounds 1 and 11 showed inhibitory effects against C. albicans secreted aspartic proteases (SAP) with IC50 of 20 and 8.5 microg/mL, respectively, while the other compounds were inactive.     

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.