Four new steroid constituents from the waste residue of fibre separation from Agave americana leaves

Three new steroidal saponins, named agamenosides H-J (1-3), and a new cholestane steroid agavegenin D (4) were isolated from the waste residue of fibre separation from Agave americana leaves, together with six known steroids. Structures of the new compounds 1-4 were deduced to be (22S,23S,24R,25S)-24-[(beta-D-glucopyranosyl)oxy]-5alpha-spirostane-3beta,6alpha,23-triol 6-O-beta-D-glucopyranoside (1), (22S,23S,24R,25S)-5alpha-spirostane-3beta,23,24-triol 24-O-beta-D-glucopyranoside (2), (22S,23S,25R,26S)-23,26-epoxy-5alpha-furostane-3beta,22,26-triol 26-O-beta-D-glucopyranoside (3), and (22S,25S)-5alpha-cholestane-3beta,16beta,22,26-tetrol (4), respectively, by means of spectroscopic analysis, including extensive 1D and 2D NMR data, and the results of hydrolytic cleavage.     

New steroidal alkaloids from Fritillaria imperialis and their cholinesterase inhibiting activities

Two new cevanine steroidal alkaloids, impericine (1) and forticine (2) along with known bases delavine (3), persicanidine A (4), and imperialine (5) were isolated from the bulbs of Fritillaria imperialis. The structures of impericine (1) [(20R,22S,25S)-5alpha-cevanin-23-ene-3beta,6beta,16beta-triol] and forticine (2) [(20S,22S,25S)-5alpha-cevanine-3beta,6beta-diol] were determined with the help of spectroscopic studies. These steroidal bases showed anti-acetylcholinesterase and anti-butyrylcholinesterase inhibitory activity.     

Pregnane- and furostane-type oligoglycosides from the seeds of Allium tuberosum

Two furostane-type steroidal oligoglycosides (1, 2), together with a new pregnane-type oligoglycoside (3), were obtained from the seeds of Allium tuberosum ROTTLER. On the basis of spectroscopic analysis, the structures of three new oligoglycosides (1-3) were elucidated as 26-O-beta-D-glucopyranosyl-(25R)-3beta,22xi,26-trihydroxyl-5alpha-furostane 3-O-beta-chacotrioside, 26-O-beta-D-glucopyranosyl-(25S)-3beta,5beta,6alpha,22xi,26-pentahydroxyl-5beta-furostane 3-O-alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranoside, and 3-O-alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl 3beta,5beta,6alpha,16beta-tetrahydroxypregnane 16-(5-O-beta-D-glucopyranoyl-4(S)-methyl-5-hydroxypentanoic acid) ester, respectively.     

Steroidal oligoglycosides from the seeds of Allium tuberosum

Three new spirostanol steroidal oligoglycosides, together with a known oligoglycoside, were obtained from the seeds of Allium tuberosum after enzymatic hydrolysis of furostanol saponin fraction by beta-glucosidase. On the basis of spectroscopic analysis, the structure of new spirostanol oligoglycosides were elucidated as (25S)-spirost-5-ene-2alpha,3beta-diol 3-O-alpha-L-rhamnopyranosyl-(1-->4)-[alpha-L-rhamnopyranosyl-(1-->2)]-be ta-D-glucopyranoside, (25S)-spirostane-3beta,5beta,6alpha-triol 3-O-alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranoside, and (25S)-5beta-spirostane-3beta,6alpha-diol 3-O-alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranoside.     

Four new 3,5-cyclosteroidal saponins from Dracaena surculosa

Further search for steroidal compounds contained in Dracaena surculosa (Agavaceae) led to the isolation of two new 3,5-cyclospirostanol saponins (1, 2) and two new 3,5-cyclofurostanol saponins (3, 4). Their structural assignment was established by spectroscopic analysis and a few chemical transformations as (24S,25R)-1beta-[(beta-D-fucopyranosyl)oxy]-6beta-hydroxy-3alpha,5alpha-cyclospirostan-24-yl beta-D-glucopyranoside (1), (24S,25R)-1beta-[(beta-D-glucopyranosyl)oxy]-6beta-hydroxy-3alpha,5alpha-cyclospirostan-24-yl beta-D-glucopyranoside (2), (25S)-1beta-[(beta-D-glucopyranosyl)oxy]-6beta-hydroxy-22alpha-methoxy-3alpha,5alpha-cyclofurostan-26-yl beta-D-glucopyranoside (3), and (25S)-1beta-[(beta-D-fucopyranosyl)oxy]-6beta-hydroxy-22alpha-methoxy-3alpha,5alpha-cyclofurostan-26-yl beta-D-glucopyranoside (4), respectively.     

Spirostanol sapogenins from the underground parts of Tupistra chinensis

Chemical examination of the underground parts of Tupistra chinensis led to the isolation of two new 5beta-spirostane type steroidal sapogenins, tupichigenin B (1) and C (2), together with two known steroidal sapogenins, ranmogenin A (3) and delta25(27)-pentrogenin (4). The structures of 1 and 2 were established as spirost-25(27)-ene-1beta,3beta,4beta,5beta,6b eta-pentaol and 1beta,2beta,3beta,4beta,5beta-pentahydroxyspi rost-25(27)-en-6-one, respectively, on the basis of detailed analysis of their physical and spectral data.     

Further bisabolenes and dammarane triterpenes of Commiphora kua resin

From the resins of Commiphora kua a novel bisabolene; 6-hydroxy-2-methyl-5-(5'-hydroxy-1'(R),5'-dimethylhex-3'-enyl)-phenol together with two new dammarane triterpenes, 3beta,16beta,20(S),25-tetrahydroxydammar-23-ene and 3beta-acetoxy-16beta,20(S),25-trihydroxydammar-23-ene, have been isolated. In addition, being reported are known compounds identified as 2-methyl-5-(4'(S)-hydroxy-1'(R),5'-dimethylhex-5'-enyl)-phenol, 2-acetoxyfuranodienone, 2-methoxyfuranodienone, 3beta,16beta,20(R)-trihydroxydammar-24-ene and its acetate derivative, 3beta-acetoxy-16beta,20(R)-dihydroxydammar-24-ene, and beta-amyrin and its acetate derivative. 2-Methyl-5-(4'(S)-hydroxy-1'(R),5'-dimethylhex-5'-enyl)-phenol displayed fungicidal activity against Cladosporium cucumernum on TLC assay.     

Six new dammarane-type triterpene saponins from the leaves of Panax ginseng

Six new minor saponins, together with known ginsenosides, were isolated from the leaves of Panax ginseng. The new saponins were named as ginsenoside-Rh5, -Rh6, -Rh7 -Rh8, -Rh9 and -Rg7, and their structures were elucidated on the basis of chemical and physicochemical evidence to be as follows: ginsenoside-Rh5: 3beta,6alpha,12beta,24zeta-tetrahydroxy-dammar-20(22),25-diene 6-O-beta-D-glucopyranoside (1), -Rh6: 3beta,6alpha12beta,20(S)-tetrahydroxy-25-hydroperoxy-dammar-23-ene 20-O-beta-D-glucopyranoside (2), -Rh7: 3beta,7beta,12beta,20(S)-tetrahydroxy-dammar-5,24-diene 20-O-beta-D-glucopyranoside (3), -Rh8: 3beta,6alpha,20(S)-trihydroxy-dammar-24-ene-12-one 20-O-beta-D-glucopyranoside (4), -Rh9: 3beta,6alpha,20(S)-trihydroxy-12beta,23-epoxy-dammar-24-ene 20-O-beta-D-glucopyranoside (5) and -Rg7: 3-O-beta-D-glucopyranosyl 3beta,12beta,20(S),24(R)-tetrahydroxy-dammar-25-ene 20-O-beta-D-glucopyranoside (6).     

Trojanosides I-K: new cycloartane-type glycosides from the aerial parts of Astragalus trojanus.

Three new cycloartane-type triterpene glycosides have been isolated from the aerial parts of Astragalus trojanus. The structures were established mainly by a combination of one- and two-dimensional NMR techniques [1H-1H-correlation spectroscopy (COSY), 1H-13C-heteronuclear multiple quantum correlation spectroscopy (HMQC), and 1H-13C-heteronuclear multiple-bond correlation spectroscopy (HMBC)] and high resolution electrospray ionization mass spectrometry (HR-ESI-MS) as 3-O-beta-(2',3'-di-O-acetyl)-D-xylopyranosyl-6-O-beta-D-glucopyranosyl-16-O- acetoxy-20(R),24(S)-epoxycycloartane-3beta,6alpha,16beta,25-tetrol, 3-0-[alpha-L-rhamnopyranosyl-(1-->2)-beta-(3',4'-di-O-acetyl)-D-xylopyranosyll-6-O-beta-D-xylopyranosyl-20(R),24(S)-epoxycycloartane-3p,6alpha,16beta,25-tetrol, 3-O-beta-D-xylopyranosyl-6,16-di-O-beta-D-glucopyranosyl-20(R)24(S)-epoxycycloartane-3beta,6alpha,16beta,25-tetrol.     

Six new withanolide-type steroids from the leaves of Solanum cilistum

Six new withanolide-type steroids, designated cilistols v, t, i, j, y and w (1-6, respectively), were obtained from the leaves of Solanum cilistum. Their respective structures were characterized by spectroscopic means as follows: Cilistol v (1) was (22R,24Z)-1alpha,3beta,22,26-tetrahydroxyergost-5,24-diene 26-O-beta-D-glucopyranoside, which is regarded as the precursor of other withanolide-type steroids included in this title plant. Cilistol t (2) was (22R,24S,25R,26S)-24,25;22,26-diepoxy-1alpha,3beta,26-trihydroxyergost-5-ene 26-O-beta-D-glucopyranoside, and cilistols j (3) and i (4) corresponded to the substances probably formed by the cleavage of the epoxy ring at C-24 and 25 of 2. Cilistol y (5) was 3-O-sulphonyl (22R,24S,25R,26R)-1-oxo-24,25; 22,26-diepoxy-3beta,17alpha,26-trihydroxyergost-5-ene 26-O-beta-D-glucopyranoside, and cilistol w (6) corresponded to the substance obtained by the fission of the epoxy ring at C-24 and 25 of 5. The occurrence of these withanolide type steroids from Solanum genera is rare and worthy of note.     

云南重楼中的新甾体皂苷

从云南重楼Paris polyphylla Sm. var. yunnanensis(France. )Hand.-Mazz.的干燥根茎中分离鉴定了4个甾体皂苷(1~4), 其中化合物1是新化合物, 采用波谱技术鉴定其结构为24-O-β-D-吡喃半乳糖基-(23S,24S)-螺甾-5, 25(27)-二烯-1β,3β,23,24-四醇-1-O-β-D-吡喃木糖基(1→6)-β-D-吡喃葡萄糖基(1→3)[α-L-吡喃鼠李糖基(1→2)]-β-D-吡喃葡萄糖苷.     

Complete (1)H and (13)C assignments of the four major saponins from Dioscorea villosa (wild yam)

Complete (1)H and (13)C spectral assignments for the four major steroidal saponins isolated by methanolic extraction of the roots of Dioscorea villosa, collected in North Carolina, United States (in summer and autumn), are presented in this paper. The structures were determined by a combination of (1)H, (13)C and 2D NMR techniques and were found to be ((3beta,25R)-26-(beta-D-glucopyranosyloxy)-22-methoxyfurost-5-en-3-yl-O-beta-D-glucopyranosyl-(1 --> 3)-O-beta-D-glucopyranosyl-(1 --> 4)-O-[alpha-L-rhamnopyranosyl-(1 --> 2)]-beta-D-glucopyranoside (1) (or methyl parvifloside), ((3beta,25R)-26-(beta-D-glucopyranosyloxy)-22 methoxyfurost-5-en-3-yl-O-alpha-L-rhamnopyranosyl-(1 --> 2)-O-[beta-D-gluco- pyranosyl-(1 --> 4)]-beta-D-glucopyranoside (2) (or methyl protodeltonin), (3beta,25R)-spirost-5-en-3-yl-O-beta-D-glucopy ranosyl-(1 --> 3)-O-beta-D-glucopyranosyl-(1 --> 4)-O-[alpha-L-rhamnopyranosyl-(1 --> 2)]-beta-D-glucopyranoside (3) (or Zingiberensis saponin I) and (3beta,25R)-spirost-5-en-3-yl-O-alpha-L-rhamnopyranosyl-(1 --> 2)-O-[beta-Ds-glucopyranosyl -(1 --> 4)]-beta-D-glucopyranoside (4) (or deltonin).     

Tomato new sapogenols, isoesculeogenin A and esculeogenin B

Two novel sapogenols, isoesculeogenin A (1) and esculeogenin B (2) of steroidal alkaloid glycosides, lycoperoside F and esculeoside B, respectively, isolated from the ripe tomato have been characterized as (5alpha,22R,23R,25S)-3beta,23,27-trihydroxyspirosolane and (5alpha,22S,23R,25S)-22,26-epimino-16beta,23-epoxy-3beta,23,27-trihydroxycholestane, respectively.     

Glycerol derivatives and sterols from Sargassum parvivesiculosum

Five glycerol derivatives (1-5) and three sterols (6-8) were isolated from the EtOH extraction of the brown alga of Sargassum parvivesiculosum. On the basis of spectroscopic methods, their structures were elucidated as 1,3-di-O-[2',2'-di-(p-phenylene) isopropylidene] glycerol (1), (2S)-1-O-heptatriacontanoyl glycerol (2), (2S)-1,2-di-O-palmitoyl-3-O-(6-sulpho-alpha-D-quinovopyranosyl) glycerol (3), (2S)-1-O-palmitoyl glycerol (4), (2S)-1,3-di-(O-palmitoyl)-2-O-octadecanoyl glycerol (5), 24-ethylcholest-5,23Z-dien-3beta,28zeta-diol (6), 24-vinylcholest-5-en-24zeta-hydroperoxy (7), 24-ethylcholest-4,24(28)-dien-3beta-ol (8), respectively. Among them, 1 and 2 were new.     

Four novel withanolide-type steroids from the leaves of Solanum cilistum.

Four novel withanolide-type steroids named cilistols p, pm, p1 and u (1-4, respectively), were isolated from the leaves of Solanum cilistum. The respective structures were characterized by spectroscopic means as follows: cilistol p (1) was (22R,24R,25R,26S)-1-oxo-22,26-epoxy-3alpha,5alpha-cycloergostane-6beta,17alpha, 24,25,26-pentaol 26-O-beta-D-glucopyranoside, cilistol pm (2) corresponded to the 6-O-methyl ether derivative of 1; cilistol p1 (3) was represented as the 24-O-methyl ether of 1, and cilistol u (4) was shown to be the epoxide between C-24 and -25, presumably bearing cilistols p, pm and p1 by ring-opening.     

Steroidal saponins from the bulbs of Allium karataviense.

Chemical examination of the bulbs of Allium karataviense led to the isolation of five new spirostanol saponins (7-11) and a new furostanol saponin (12), together with a known steroidal sapogenin (1) and five known saponins (2-6). The structures of the new saponins were determined by detailed analysis of their spectral data, including two-dimensional NMR spectroscopy. The steroidal saponins produced by A. karataviense, except for 5 and 6, were found to be based upon (25R)-5 alpha-spirostane-2 alpha,3 beta,5,6 beta-tetrol (alliogenin) and contain a beta-D-glucopyranosyl moiety with the formation of an O-glycoside linkage to C-2 of the polyhydroxylated steroidal skeleton as the common structural feature. The isolated compounds were evaluated for cytostatic activity against human promyelocytic leukemia HL-60 cells.     

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.     

Structures of two new steroidal glycosides, soladulcosides A and B from Solanum dulcamara

The structures of two new steroidal glycosides named soladulcosides A and B, isolated from the aerial parts of Solanum dulcamara including new sapogenols, were elucidated as (22R, 25R)-3 beta, 15 alpha, 23 alpha-trihydroxy-5 alpha-spirostan-26-one 3-O-alpha-L-rhamnopyranosyl-(1----2)-beta-D-glucopyranoside and (22R, 25R)-3 beta,23 alpha-dihydroxy-5 alpha-spirostan-26-one 3-O-alpha-L-rhamnopyranosyl-(1----2)-[alpha-L-rhamnopyranosyl-(1----4)]- beta-D-glucopyranoside, respectively.     

New cholinesterase inhibiting steroidal alkaloids from the leaves of Sarcococca coriacea of Nepalese origin

From the leaves of Sarcococca coriacea two new steroidal alkaloids, epoxynepapakistamine-A [(20S)-20-(N-methylamino)-3beta-(tigloylamino)-5alpha-pregna-16alpha,17alpha-epoxy-2beta,4beta-di-O-acetate] (1), and epoxysarcovagenine-D [(20S)-20-(N-methylamino)-3beta-(tigloylamino)-5alpha-pregna-2-en-16alpha,17alpha-epoxy-4-one] (2), and two known compounds funtumafrine C [(20S)-20-(N,N-dimethylamino)-5alpha-pregna-3-one] (3) and N-methylfuntumine (4) were isolated. Their structures were elucidated on the basis of their spectral properties. The compounds 1, 3 and 4 were found to have cholinesterase inhibitory activity when tested for the inhibition of electric eel acetylcholinesterase and horse serum butyrylcholinesterase. They inhibited both enzymes in a concentration dependent fashion.     

Five new nortropane alkaloids and six new amino acids from the fruit of Morus alba LINNE growing in Turkey

Investigation of the constituents of the fruits of Morus alba LINNE (Moraceae) afforded five new nortropane alkaloids (1-5) along with nor-psi-tropine (6) and six new amino acids, morusimic acids A-F (7-12). The structures of the new compounds were determined to be 2alpha,3beta-dihydroxynortropane (1), 2beta,3beta-dihydroxynortropane (2), 2alpha,3beta,6exo-trihydroxynortropane (3), 2alpha,3beta,4alpha-rihydroxynortropane (4), 3beta,6exo-dihydroxynortropane (5), (3R)-3-hydroxy-12-[(1S,4S)-4-[(1S)-1-hydroxyethyl]-pyrrolidin-1-yll-dodecanoic acid-3-O-beta-D-glucopyranoside (7), (3R)-3-hydroxy-12-[(1S,4S)-4-[(1S)-1-hydroxyethyl]-pyrrolidin-1-yll-dodecanoic acid (8), (3R)-3-hydroxy-12-1(1R,4R,5S)-4-hydroxy-5-methyl-piperidin-1-yll-dodecanoic acid-3-O-beta-D-glucopyranoside (9), (3R)-3-hydroxy-12-[(1R,4R,5S)-4-hydroxy-5-methyl-piperidin-1-yll-dodecanoic acid (10), (3R)-3-hydroxy-12-[(1R,4R,5S)-4-hydroxy-5-hydroxymethyl-piperidin-1-yl]-dodecanoic acid-3-O-beta-D-glucopyranoside (11), and (3R)-3-hydroxy-12-[(1R,4S,5S)-4-hydroxy-5-methyl-piperidin-1-yl]-dodecanoic acid (12) on the basis of spectral and chemical data.