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.     

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).     

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.     

Cimiracemosides I-P,new 9,19-cyclolanostane triterpene glycosides from Cimicifuga racemosa

Eight new and 13 known triterpene glycosides, along with the known compounds glyceryl-1-palmitate and daucosterol-6'-linoleate were isolated from the roots/rhizomes of Cimicifuga racemosa. The new compounds, designated as cimiracemosides I-P (1, 3-9), were determined by spectral analysis to be 7-dehydro-23-epi-12,26-dideoxyacteol-3-O-beta-D-xylopyranoside (1), 12-O-acetyl-25-anhydrocimigenol-3-O-alpha-L-arabinopyranoside (3), 12-O-acetyl-25-anhydrocimigenol-3-O-beta-D-xylopyranoside (4), 4',23-O-diacetylshengmanol-3-O-beta-D-xylopyranoside (5), 4',23-O-diacetylshengmanol-3-O-alpha-L-arabinopyranoside (6), 23-epi-acetylacteol-3-O-alpha-L-arabinopyranoside (7), 4'-O-acetyl-26-deoxyactein (8), and 16beta:23;24:25-diepoxy-12beta-O-acetyl-3beta-hydroxy-9,19-cyclolanost-23,26-olide-O- beta-D-xylopyranoside (9).     

Two new cyclolanostanol xylosides from the aerial parts of Cimicifuga dahurica

From the aerial parts of Cimicifuga dahurica, two new cyclolanostanol xylosides, cimilactone A (1) and cimilactone B (2), and three known compounds were isolated. On the basis of spectral and chemical evidence, the structures of 1 and 2 were determined to be 12beta-acetoxy-3beta-O-D-xylopyranosyloxy-24,25,26,27-tetranor-9,19-cyclolanost-16,23-lactone (1) and 12beta-acetoxy-3beta-O-D-xylopyranosyloxy-24,25,26,27-tetranor-9,19-cyclolanost-7-ene-16,23-lactone (2). The known compounds were identified as cimigenol 3-O-beta-D-xylopyranoside, 23-O-acetylshengmanol-3-O-beta-D-xylopyranoside, and 25-O-acetylcimigenol-3-O-beta-D-xylopyranoside, respectively.     

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.     

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.     

Secondary metabolites from the roots of Astragalus zahlbruckneri

Four new phenolic glycosides, beta-apiofuranosyl-(1-->2)-beta-glucopyranosides (1-4), along with the cycloartane triterpenes 20(R),25-epoxy-3beta,6alpha,16beta,24alpha-tetrahydroxycycloartane (5) and 20(R),24(S)-epoxy-3beta,6alpha,25-trihydroxycycloartan-16-one (6) were isolated from roots of Astragalus zahlbruckneri. The structure elucidation of all compounds was based on their (1)H and (13)C NMR spectral data including 1D-TOCSY, DQF-COSY, HSQC, and HMBC experiments.     

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.     

New dammarane and malabaricane triterpenes from Caloncoba echinata

Three novel triterpenes, (11R,20R)-11,20-dihydroxy-24-dammaren-3-one (1), (17S,20R,24R)-17,25-dihydroxy-20,24-epoxy-14(18)-malabaricen-3-one (2), and (17R,20S,24R)-17,25-dihydroxy-20,24-epoxy-14(18)-malabaricen-3-one (3), were isolated from leaves of Caloncoba echinata. The structures were established using mainly 800 MHz NOESY and HMBC connectivities. The absolute stereochemistry of C-11 in 1 and that of C-17 in 2 were established by the Mosher method. The stereochemistry of the side chains of the malabaricanes is compatible with their biosynthesis by a cascade opening of diepoxides. The isolated triterpenes inhibited growth of Plasmodium falciparum parasites in vitro apparently via incorporation into erythrocyte membrane, as suggested by transformation of erythrocytes into stomatocytes at a concentration level at which the growth inhibition was observed.     

Cytotoxic withaphysalins from the leaves of Acnistus arborescens

Three withaphysalins, rel-(17S,20R,22R)-5 beta,6 beta:18,20-diepoxy-4 beta-hydroxy-1,18-dioxowitha-2,24-dienolide(withaphysalin M) (1), rel-(17S,20R,22R)-5 beta,6 beta:18,20-diepoxy-4 beta-hydroxy-18-ethoxy-1-oxowitha-2,24-dienolide (withaphysalin F ethyl ether, withaphysalin O) (2), and rel-(17S,20R,22R)-5 beta,6 beta:18,20-diepoxy-4 beta-hydroxy-1,18-dioxowitha-24-enolide (withaphysalin N) (3), were isolated from the leaves of Acnistus arborescens. The structures were deduced from 1D ((1)H NMR, (13)C NMR, DEPT-(13)C NMR) and 2D (COSY, HMQC, HMBC) NMR analysis and the relative stereochemical assignments based on 1D NOESY correlations and analysis of coupling constants. Compounds 1 and 2 displayed potent cytotoxic activity against a panel of human cancer cell lines.     

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.     

Neocimicigenosides A and B, cycloartane glycosides from the rhizomes of Cimicifuga racemosa and their effects on CRF-stimulated ACTH secretion from AtT-20 cells

Two new cycloartane glycosides, named neocimicigenosides A (1) and B (2), were isolated from the rhizomes of Cimicifuga racemosa. The structures of 1 and 2 were determined on the basis of extensive spectroscopic analysis and enzymatic hydrolysis followed by chromatographic and spectroscopic analyses to be (16S,23R,24S)-24-acetoxy-16,23:16,25-diepoxy-15alpha-hydroxycycloartan-3beta-yl alpha-L-arabinopyranoside (1) and (16S,23R,24S)-24-acetoxy-16,23:16,25-diepoxy-15alpha-hydroxycycloartan-3beta-yl beta-D-xylopyranoside (2), respectively. Neocimicigenosides A and B enhanced CRF-stimulated ACTH secretion from AtT-20 cells.     

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.     

Cytotoxic cycloartane triterpene saponins from Actaea asiatica

Three new 9,19-cycloartane triterpene glycosides, asiaticoside A (1), asiaticoside B (2), and 25-O-ethylcimigenol-3-O-beta-D-xylopyranoside (3), together with cimiacemoside I (4), 25-O-acetylcimigenol-3-beta-O-D-xyloside (5), and 25-anhydrocimigenol-beta-O-D-xyloside (6) were isolated from the roots/rhizomes extract of Actaea asiatica, and their structures were established by spectroscopic methods (IR, HRESIMS, and NMR). Compounds 1-3, 5, and 6 had notable cytotoxicity against HepG2 and MCF-7 cancer cell lines.     

Sesquiterpene lactones from Lychnophora ericoides

Two new sesquiterpene lactones, (4S,6R,7S,8S,10R,11S,16R)-1-oxo-3(10),8(16)-diepoxy-16-methylprop-1Z-enyl-16-methoxygermacra-2-en-6(12)-olide (1) and (4S,6R,7S,8S,10R,11S)-1-oxo-3,10-epoxy-8-angeloyloxygermacra-2-en-6(12)-olide (2), were isolated from Lychnophora ericoides. Their structures, including absolute configuration, were established by spectroscopic methods, including single-crystal X-ray analysis. Monitoring the furanoheliangolide metabolism of L. ericoides revealed an increase in biosynthesis during the plant flowering period.     

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.     

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.     

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.