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.     

Pregnane glycosides and steroid saponins from Smilax bockii Warb. and their NGF-potentiating activity

The chemical constituents of the roots of Smilax bockii Warb. were investigated and two pregnane glycosides and three steroid saponins were isolated. Their structures were established as 3beta-hydroxypregna-5,16-dien-20-one-3-O-alpha-L-rhamnopyranosyl(1 --> 4)-alpha-L-rhamnopyranosyl(1 --> 4)-[alpha-L-rhamnopyranosyl(1 --> 2)]-beta-D-glucopyranoside (1), 3beta-hydroxypregna-5,16-dien-20-one-3-O-alpha-L-rhamnopyranosyl(1 --> 2)-[alpha-L-rhamnopyranosyl(1 --> 4)]-beta-D-glucopyranoside (2), dioscin (3), methyl protodioscin (4), 26-O-beta-D-glucopyranosyl-22alpha-methoxyl-(25R)-furost-5-en-3beta, 26-diol 3-O-alpha-L-rhamnopyranosyl(1 --> 4)-alpha-L-rhamnopyranosyl(1 --> 4)-[alpha-L-rhamnopyranosyl(1 --> 2)]-beta-D-glucopyranoside (5) on the basis of spectral analysis and chemical methods. Compound 1 is a new natural product and compounds 2, 5 were first isolated from the genus Smilax. Compound 5 showed enhancing activity of nerve growth factor (NGF)-induced neurite outgrowth in PC 12D cells.     

Studies on Balanites aegyptiaca fruits, an antidiabetic Egyptian folk medicine

An aqueous extract of mesocarps of the fruits of Balanites aegyptiaca exhibited a prominent antidiabetic activity by oral administration in streptozotocin induced diabetic mice. From one of the active fractions of this extract, two new steroidal saponins were isolated, and their structures were determined as 26-O-beta-D-glucopyranosyl-(25R)-furost-5-ene-3 beta,22,26-triol 3-O-[alpha-L-rhamnopyranosyl-(1----2)]-[beta-D-xylopyranosyl-(1---- 3)]-[alpha-L-rhamnopyranosyl-(1----4)]-beta-D-glucopyranoside and its 22-methyl ether. In addition, two known saponins, 26-O-beta-D-glucopyranosyl-(25R)-furost-5-ene-3 beta,22,26-triol 3-O-(2,4-di-O-alpha-L-rhamnopyranosyl)-beta-D-glucopyranoside and its methyl ether were isolated and identified. It was revealed that the individual saponins did not show antidiabetic activity, while the recombination of these saponins resulted in significant activity. From an ethanolic extract of the epicarps, two known flavonol glycosides, isorhamnetin-3-O-robinobioside and isorhamnetin-3-O-rutinoside were isolated and identified.     

New furostanol saponins from Allium ascalonicum L

An analysis of the polar extracts from Allium ascalonicum L. led to the isolation of two new furostanol saponins (compound 1 and 2) and two known furostanol saponins (compound 3 and 4). On the basis of 1D and 2D NMR (including (1)H, (13)C NMR, (1)H--(1)H COSY, HSQC, TOCSY, HMBC, and NOESY), FAB-MS spectrometry, and chemical methods, their structures were elucidated as (25R)-26-O-beta-D-glucopyranosyl-22-hydroxy-5alpha-furost-2-one-3beta, 5, 6beta, 26-tetraol-3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranoside (ascalonicoside C, 1), (25R)-26-O-beta-D-glucopyranosyl-22-methoxy-5alpha-furost-2-one-3beta, 5, 6beta, 26-tetraol- 3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranoside (ascalonicoside D, 2), (25R)-26-O-beta-D-glucopyranosyl-22-hydroxy-5-ene-furostan-3beta, 26-diol-3-O-alpha-L-rhamnopyranosyl-(1-->4)-alpha-L-rhamnopyranosyl-(1-->4)-[alpha-L-rhamnopyranosyl-(1-->2)]-beta-D-glucopyranoside (dichotomin, 3), and (25R)-26-O-beta-D-glucopyranosyl-22-hydroxy-5-ene-furostan-3beta, 26-diol-3-O-alpha-L-rhamnopyranosyl-(1-->2)-[alpha-L-arabinofuranosyl-(1-->4)]-beta-D- glucopyranoside (parisaponin I, 4).     

Medicinal foodstuffs. XXVII. Saponin constituents of gotu kola (2): structures of new ursane- and oleanane-type triterpene oligoglycosides, centellasaponins B, C, and D, from Centella asiatica cultivated in Sri Lanka

Ursane- and oleanane-type triterpene oligoglycosides, centellasaponins B, C, and D, were isolated from the aerial parts of Centella asiatica (L.) Urban cultivated in Sri Lanka together with madecassoside, asiaticoside, asiaticoside B, and sceffoleoside A. The chemical structures of centellasaponins B, C, and D were determined on the basis of chemical and physicochemical evidence to be madecassic acid 28-O-beta-D-glucopyranosyl(1-->6)-beta-D-glucopyranoside, madasiatic acid 28-O-alpha-L-rhamnopyranosyl(1-->4)-beta-D-glucopyranosyl(1-->6)-beta-D-glucopyranoside, and 3beta,6beta,23-trihydroxyolean-12-en-28-oic acid 28-O-alpha-L-rhamnopyranosyl(1-->4)-beta-D-glucopyranosyl(1-->6)-beta-D-glucopyranoside, respectively.     

Medicinal foodstuffs. XXII. Structures of oleanane-type triterpene oligoglycosides, pisumsaponins I and II, and kaurane-type diterpene oligoglycosides, pisumosides A and B, from green peas, the immature seeds of Pisum sativum L

Two new oleanane-type triterpene oligoglycosides, pisumsaponins I and II, and two new kaurane-type diterpene oligoglycosides, pisumosides A and B, were isolated from the immature seeds (green peas) of Pisum sativum L. together with soyasaponin I, bersimoside I, dehydrosoyasaponin I, and their 6'-methyl esters. The structures of pisumsaponins and pisumosides were determined on the basis of chemical and physicochemical evidence as 22-O-malonylsoyasapogenol B 3-O-alpha-L-rhamnopyranosyl(1-->2)-beta-D-galactopyranosyl(1-->2)-beta-D-glucopyranosiduronic acid (22-O-malonylsoyasaponin I), sandosapogenol 3-O-alpha-L-rhamnopyranosyl(1-->2)-beta-D-galactopyranosyl(1-->2)-beta-D-glucopyranosiduronic acid, 17-O-beta-D-glucopyranosyl-6beta,7beta,13gamma,17-tetrahydroxy-19-kauranoic acid 19-O-beta-D-glucopyranosyl(1-->2)-beta-D-glucopyranoside, and 6beta,7beta,13beta,17-tetrahydroxy-19-kauranoic acid 19-O-beta-D-glucopyranosyl(1-->2)-beta-D-glucopyranoside, respectively.     

Steroids of the spirostan and furostan series from Nolina microcarpa I. Structures of nolinospiroside C and nolinofurosides A and C

In addition to the know steroid sapogenin (25S)-ruscogenin (I), three new glycosides have been isolated from the leaves ofNolina microcarpa S. Wats. (family Dracaenacea), and the following structures are suggested for them: (25S)-spirost-5-ene-1β,3β-diol 1-O-β-D-fucopyranoside (nolinospiroside C, II), (25S)-furost-5-ene-1β,3β,22α,26-tetraol 1-O-β-D-fucopyranoside (nolinofuroside A, III), and (25S)-furost-5-ene-1β, 3β, 22α, 26-tetraol 1-O-β-D-fucopyranoside 26-O-β-D-glucopyranoside (nolinofuroside C, V).     

A new steroidal saponin from Dioscorea cayenensis

The new 26-O-beta-D-glucopyranosyl-3beta,26-dihydroxy-20,22-seco-25(R)-furost-5-en-20,22-dione-3-O-alpha-L-rhamnopyranosyl-(1-->4)-alpha-L-rhamnopyranosyl-(1-->4)-[alpha-L-rhamnopyranosyl-(1-->2)]-beta-D-glucopyranoside (1), along with the known methyl protodioscin (2), asperoside (3) and prosapogenin A of dioscin (4) were isolated from the rhizomes of Dioscorea cayenensis LAM.-HOLL (Dioscoreaceae). Their structures were established mainly on the basis of 600 MHz 2D-NMR spectral data. 4 exhibited antifungal activity against the human pathogenic yeasts Candida albicans, C. glabrata and C. tropicalis (MICs of 20.8, 6.25, 25 microg/ml, respectively), whereas saponins 1-3 were inactive.     

Triterpene glycosides from the bark of Robinia pseudo-acacia L. I.

From the bark of Robinia pseudo-acacia L., five new triterpene glycosides, robiniosides A-D (3, 5-7) and compound III (4), were isolated and their structures were elucidated as 3-O-alpha-L-rhamnopyranosyl(1-->2)-beta-D-glucopyranosyl(1-->2)-beta-D- glucuronopyranosyl 3 beta,22 beta-dihydroxyolean-12-en-29-oic acid (3), 3-O-alpha-L-rhamnopyranosyl(1-->2)-beta-D-galactopyranosyl(1-->2)-beta-D -glucuronopyranosyl 3 beta,22 beta,24-trihydroxyolean-12-en-29-oic acid (4), whose sapogenol was unambiguously characterized and designated as oxytrogenin, 3-O-alpha-L-rhamnopyranosyl(1-->2)-beta-D-glucopyranosyl(1-->2)-beta-D glucuronopyranosyl oxytrogen (5), 3-O-alpha-L-rhamnopyranosyl(1-->2)-beta-D galactopyranosyl(1-->2)-beta-D-glucuronopyranosyl oxytrogenin 22-O-alpha-L-rhamnopyranoside (6), 3-O-alpha-L- rhamnopyranosyl(1-->2)-beta-D-glucopyranosyl(1-->2)-beta-D-glucuronop yranosyl oxytrogenin 22-O-alpha-L-rhamnopyranoside (7), respectively, together with two known triterpene glycosides, kaikasaponin III (1) and 3-O-alpha-L-rhamnopyranosyl(1-->2)-beta-D-galactopyranosyl(1-->2)-beta-D - glucuronopyranosyl 3 beta,22 beta-dihydroxyolean-12-en-29-oic acid (2).     

Steroids of the furostan and spirostan series from Nolina microcarpa II. structures of nolinospiroside D and nolinofurosides D,E, and F

In addition to the know steroid sapogenin (25S)-ruscogenin (I), three new glycosides have been isolated from the leaves ofNolina microcarpa S. Wats. (family Dracaenacea), and the following structures are suggested for them: (25S)-spirost-5-ene-1β,3β-diol 1-O-β-D-fucopyranoside (nolinospiroside C, II), (25S)-furost-5-ene-1β,3β,22α,26-tetraol 1-O-β-D-fucopyranoside (nolinofuroside A, III), and (25S)-furost-5-ene-1β, 3β, 22α, 26-tetraol 1-O-β-D-fucopyranoside 26-O-β-D-glucopyranoside (nolinofuroside C, V). M. V. Frunze Simferopol' State University. Institute of Chemistry of Plant Substances, Uzbek Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 672–678, September–October, 1991.     

Four new cycloartane glycosides from Thalictrum fortunei

Four new cycloartane glycosides were isolated from the aerial parts of Thalictrum fortunei (Ranunculaceae). The chemical structures of these new glycosides were elucidated as 3-O-beta-D-glucopyranosyl-(1-->4)-beta-D-fucopyranosyl (22S,24Z)-cycloart-24-en-3beta,22,26-triol 26-O-beta-D-glucopyranoside, 3-O-beta-D-glucopyranosyl-(1-->4)-beta-D-fucopyranosyl (22S,24Z)-cycloart-24-en-3beta,22,26-triol 26-O-beta-D-quinovopyranosyl-(1-->6)-beta-D-glucopyranoside, 3-O-beta-D-glucopyranosyl-(1-->4)-beta-D-fucopyranosyl (22S,24Z)-cycloart-24-en-3beta,22,26-triol 26-O-beta-D-xylopyranosyl-(1-->6)-beta-D-glucopyranoside, and 3-O-beta-D-glucopyranosyl-(1-->4)-beta-D-fucopyranosyl (22S,24Z)-cycloart-24-en-3beta,22,26-triol 26-O-alpha-L-arabinopyranosyl-(1-->6)-beta-D-glucopyranoside by extensive NMR methods, HR-ESI-MS, and hydrolysis. This is the first report of (22S,24Z)-3beta,22,26-trihydroxycycloartan-24-ene (thelictogenin A, 5) being glycosylated at C-26.     

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).     

Two new steroidal saponins from "Gualou-xiebai-baijiu-tang" consisting of Fructus trichosanthis and Bulbus allii macrostemi

Two new steroidal saponins were isolated from the Chinese folk medicine called Gualou-xiebai-baijiu-tang. The structures were determined to be spirost 25(27)-ene-2beta,3beta-diol-3-O-beta-D-glucopyranosyl(1-->2)-beta-D-galactopyranoside and 26-O-beta-D-glucopyranosyl-22alpha-hydroxy-5beta-furost-25(27)-ene-1beta,3beta,6beta,26-tetraol-3-O-beta-D-galactopyranoside, respectively, based on chemical evidences and spectral analysis.     

Two new steroidal glucosides from Ophiopogon.japonicus （L.f.） Ker-Gawl

Two new steroidal glucosides, 26-O-β-D-glucopyranosyl （25S）-furost-5-ene-1β,3β,22α,26-tetraol l-O-β-D-xylopyranosyl- （1 → 3）-[α-h-rhamnopyranosyl-（1 → 2）]-[β-D-fueopyranoside and （25R） spirost-5-ene-3β,14α-diol-3-β-O-β-L-rhanmopyranosyl- （1 → 2）-[β-D-xylopyranosyl（1 → 4）]-[-β-D-glucopyranoside, were isolated from the Ophiopogon japonicus （L.f.） Ker-Gaw. Their structures were elucidated by spectroscopic methods.     

Bioactive saponins and glycosides. XVI. Nortriterpene oligoglycosides with gastroprotective activity from the fresh leaves of Euptelea polyandra Sieb. et Zucc. (1): structures of Eupteleasaponins I, II, III, IV, V, and V acetate

The saponin fraction from the fresh leaves of Euiptelea polyandra Sieb. et Zucc. was found to exhibit potent gastroprotective activity. Fourteen new nortriterpene saponins called eupteleasaponins were isolated from the saponin fraction with gastroprotective activity. The structures of eupteleasaponins I, I1, III, IV, V, and V acetate were determined on the basis of chemical and physicochemical evidence as 3-O-alpha-L-rhamnopyranosyl(1-->2)-beta-D-glucopyranosyl(1 -->3)-beta-D-xylopyranosylakebonoic acid 28-O-beta-D-glucopyranosyl ester, 3-O-alpha-L-rhamnopyranosyl(1-->2)-[alpha-L-rhamnopyranosyl(1 -->4)-beta-D-glucopyranosyl(1-->3)-beta-D-xylopyranosylakebonoic acid 28-O-beta-D- D-glucopyranosyl(1-->3)-beta-D-xylopyranosylakebonoic acid 28-O-beta-D-glucopyranosyl ester, 3-O-alpha-L-rhamnopyranosyl(1-->2)-alpha-L-rhamnopyranosyl(1 -->4)-beta-D-glucopyranosyl(1-->3)-beta-D-xylopyranosylakebonoic acid 28-O-beta-D-glucopyranosyl ester, 3-O-alpha-L-rhamnopyranosyl(1 -->2)-[alpha-L-arabinopyranosyl(1-->4)-alpha-L-rhamnopyranosyl(1-- >4)]-beta-D- glucopyranosyl(1-->3)-beta-D-xylopyranosylakebonoic acid 28-O-beta-D-glucopyranosyl ester, 3-O-alpha-L-rhamnopyranosvl(1-->2)-[alpha-L-arabinopyranosyl (1 -->4)-beta-L-rhamnopyranosyl(1 -->4)]-beta-D-glucopyranosyl(1 -->3)-beta-D-xylopyranosylakebonoic acid, 3-O-alpha-L-rhamnopyranosyl(1 -->2)-beta-D-glucopyranosvl(1-->3)-beta-D-xylopyranosyleupteleo genin, and 3-O-alpha-L-rhamnopyranosyl(1-->2)-6"-O-acetyl-gamma-D-glucopyranosyl(1 -->3)-beta-D-xylopyranosyleupteleogenin.     

Studies on the constituents of solanaceous plants. (46). Steroidal glycosides from the fruits of Solanum anguivi

Three new glycosides named anguiviosides A-C were isolated from the fruits of Solanum anguivi and characterized as follows:3-O-beta-chacotrioside (1), 3-O-[4-O-maloyl-alpha-L-rhamnopyranosyl(1-->2)]-alpha-L-rhamnopyra nosyl(1-->4)-beta-D-glucopyranoside (2) and 3-O-alpha-L-rhamnopyranosyl(1-->2)-beta-D-xylopyranosyl(1-->3)]-beta-D-+ ++glucopyranoide (3), of (25R,26R)-spirost-5-en-3beta,26-diol.     

Three new steroidal saponins from the rhizome of Paris polyphylla

A mixture of a pair of stereoisomeric new spirostanol saponins (1a and 1b) and a new cholestane saponin (2) were isolated from the rhizome of Paris pollyphylla Smith var. yunnanensis. Their structures were elucidated as (25R)-spirost-5-en-3beta, 7beta-diol-3-O-alpha-L-arabinofuranosyl-(1 --> 4)-[alpha-L-rhamnopyranosyl-(1 --> 2)]-beta-D-glucopyranoside (1a), (25R)-spirost-5-en-3beta, 7alpha-diol-3-O-alpha-L-arabinofuranosyl-(1 --> 4)-[alpha-L-rhamnopyranosyl-(1 --> 2)]-beta-D-glucopyranoside (1b) and 26-O-beta-D-glucopyranosyl-(25R)-Delta(5(6), 17(20))-dien-16, 22-dione-cholestan-3beta, 26-diol-3-O-alpha-L-arabinofuranosyl-(1 --> 4)-[alpha-L-rhamnopyranosyl-(1 --> 2)]-beta-D-glucopyranoside (2) by a combination of HR-ESI-MS, FAB-MS, 1D and 2D NMR techniques (including (1)H-NMR, (13)C-NMR, (1)H--(1)H COSY, HSQC, HMBC and NOESY).     

Total synthesis of methyl protodioscin: a potent agent with antitumor activity

Methyl protodioscin (1), otherwise known as 3-O-[alpha-L-rhamnopyranosyl-(1-->2)-[alpha-L-rhamnopyranosyl-(1-->4)]-beta-d-glucopyranosyl]-26-O-[beta-D-glucopyranosyl]-22-methoxy-25(R)-furost-5-ene-3 beta,26-diol, has been synthesized for the first time from diosgenin through nine steps in an overall yield of 7.8%.     

Two new triterpenoid saponins from Aralia subcapitata

Two new oleanane-type saponins, subcapitatoside B and C were isolated from the roots of Aralia subcapitata. On the basis of chemical and spectral evidences, subcapitatoside B and C were established as oleanolic acid 3-O-beta-D-glucopyranosyl-(l-->3)-[beta-D-galactopyranosyl- (1-->2)]-beta-D3--galactopyranoside, and 3-O-beta-D-glucopyranosyl- (1-->3)-[beta-D-galactopyranosyl-(1-->2)]-beta-D-glucopyranosyl oleanolic acid 28-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranoside, respectively.     

New triterpenoid saponins from Stelmatocrypton khasianum

Four new triterpenoid saponins, designated as stelmatotriterpenosides E-H (1-4), together with three known compounds, asterbatanoside B (5), 2alpha,3beta,19alpha,23-tetrahydroxy-olean-12-en-28-oic acid-3-O-beta-D-glucopyranosyl-28-O-beta-D-glucopyranosyl ester (6) and 2alpha,3beta,19alpha,23-tetrahydroxy-urs-12-en-28-oic acid-3-O-beta-D-glucopyranosyl-28-O-beta-D-glucopyranosyl ester (7), were isolated from the stems of Stelmatocrypton khasianum. On the basis of chemical and spectral evidence, the structures of 1-4 were established as 2alpha,3beta,23-trihydroxy-olean-12-en-28-oic acid-3-O-beta-D-glucopyranosyl-28-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester (1), 2alpha,3beta,23-trihydroxy-urs-12-en-28-oic acid-3-O-beta-D-glucopyranosyl-28-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester (2), 2alpha,3beta,19alpha-trihydroxy-urs-12-en-28-oic acid-3-O-beta-D-glucopyranosyl-28-O-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosyl ester (3), and 2beta,3beta,19alpha-trihydroxy-urs-12-en-24,28-dioic acid-24-O-beta-D-glucopyranosyl-28-O-beta-D-glucopyranosyl diester (4).