Spirostanol Glycosides Research Articles

Spirostanols obtained by cyclization of pseudosaponin derivatives and comparison of anti-platelet agglutination activities of spirostanol glycosides

Naturally occurring saponins 3 and 4 have a normal type F ring and α-arranged CH 3-21 group. Treatments of pseudosaponin peracetates 18 and 19 derived from 3 and 4, respectively, with alcoholic KOH, followed by acidification with acetic acid, gave spirostanols 20 and 22 having iso type F rings as major products. Structural analyses of sapogenins and saponins derived from pseudo derivatives 11, 12, 18 and 19 were performed by comparisons of their 1H-NMR spectral data and the X-ray analytical data of 3- O- p-bromobenzoyl sarsasapogenin 7, 3- O-acetyl diosgenin 13 and saponin 20. The mechanisms of ring-closure reaction of the side chain at C-22 of pseudosapogenins and pseudosaponins were deduced using stereomodels of the spirostanols derived from 11 under various reaction conditions. Inhibitory activities of saponin diglycosides 3, 4, 20, 21 and 25 on human platelet agglutinations induced by ADP and ristocetin were compared.

Anti-herpes virus activity of Solanum steroidal glycosides.

Since some Solanum-genus plants have traditionally been used for anti-cancer and anti-herpes agents from olden times, we examined anti-herpes simplex virus type 1 (HSV-1) activity of typical steroidal glycosides with the frameworks of spirostane (including nuatigenin glycoside), furostane, solasodane, tomatidane and ergostane (including dimer) obtained from Solanum plants. Among these steroidal glycosides, the spirostanol glycosides were most effective. An inclination was observed for the potency of activity to decrease in the order of spirostane, tomatidane, ergostane, solasodane, nuatigenin type, dimer of ergostane and furostane. It was also suggested that the activity depends on the kind of oligosacchride moiety.

Purification and characterization of furostanol glycoside 26- O- β-glucosidase from Costus speciosus rhizomes

In plants, spirostanol glycosides (steroid saponins) are known to be formed from furostanol glycosides during postharvest treatment and storage. Furostanol glycoside 26- O- β-glucosidase (F26G) involved in this conversion was purified to apparent homogeneity for the first time from Costus speciosus rhizomes which accumulate these glycosides. The enzyme was highly specific for cleavage of the C-26-bound glucose moiety of furostanol glycosides showing K m for protogracillin of 50 μM. Glucono-1,5-lactone, a typical β-glucosidase inhibitor, and diosgenin, an aglycone of spirostanol glycosides, strongly inhibited the enzyme activity. The purified F26G is dimeric with a native apparent molecular weight of 110,000 consisting of subunits of 54,000 and 58,000. The N-terminal sequence of the 54,000 protein has a high similarity to the sequences found in N-terminal regions of known plant β-glucosidases.

Purification and characterization of a beta-glucosidase which converts furostanol glycosides to spirostanol glycosides from Costus speciosus.

In plants, spirostanol glycosides are known to be formed from furostanol glycosides during post-harvest treatment and storage.1 Although the biological activities of these glycosides have been well described,2,3 little is known about their physiological roles in intact plants.

Spirostanol glycosides from Peliosanthes sinica.

Three new spirostanol glycosides, peliosanthosides A--C, were isolated from the whole plants of Peliosanthes sinica, along with two known ones. Their structures were elucidated by means of chemical and spectral evidence.

Study on the solanacenous plants. Part 29. Steroidal Glycosides from Solanum dulcamara.

From the aerial parts of Solanum dulcamara, two spirostanol glycosides (1 and 2) and two new spirosolane glycosides (3 and 4) were isolated and their chemical structures were characterized as tigogenin 3-O-β-solatrioside, degalactotigonin, soladulcidine 3-O-β-chacotrioside (named soladulcine A), and soladulcidine 3-O-β-lycotetraoside (named soladulcine B), respectively.

A screen for inhibitors of DNA recombination: identification of two new spirostanol glycosides from Chamaedorea linearis.

Two new glycosides have been isolated from the MeOH extract of the stem wood and stem bark of an Ecuadorian plant Chamaedorea linearis, and their structures have been determined by spectroscopic means and X-ray analysis of the aglycone to be 1-O-[beta-L-fucopyranosyl-(4'-sulfate)]-25R,5 alpha-spirostane-1 beta, 3 beta-diol [1]) and 1-O-[beta-L-fucopyranosyl-(4'-sulfate)]-25R,5 alpha-spirostane-1 alpha, 3 beta-diol [2]. These compounds were identified in a screen for inhibitors of recombinational DNA repair. Cytotoxic activity was also demonstrated.

Steroid glycosides from Polygonatum prattii

Investigation of the roots of Polygonatum prattii afforded three new steroid glycosides, paratiosides A–C, and three new prosapogenins, pratiosides D 1, E 1 and F 1. The latter three, which were obtained from the enzymatic hydrolysis products of a glycoside mixture, are considered to be the corresponding spirostanol glycosides of their proto-type furostanol ones in the plant. The structures of these compounds were established by chemical and spectral methods. It is noted that pratioside C possessing a 3,27-di- O-sugar chain is the first example to be isolated from a natural source.

Ruscus aculeatusExtract: Unambiguous Proof of the Absorption of Spirostanol Glycosides in Human Plasma after Oral Administration

<i>Ruscus aculeatus</i>Extract: Unambiguous Proof of the Absorption of Spirostanol Glycosides in Human Plasma after Oral Administration

Steroid glycosides of the roots ofCapsicum annuum. II. The structure of the capsicosides

Two tigogenin glycosides and two diosgenin glycosides have been isolated from a methanolic extract of the roots of bush red pepper. An attempt to isolate the individual spirostanol glycosides directly was unsuccessful. These compounds have very similar structures. For their separation, acetylation and epoxidation of the double bond of the aglycon, diosgenin, in the corresponding glycosides was performed. The derivatives obtained were purified by chromatography. To establish the complete chemical structure of each capsicoside we used both chemical and physical methods; complete and partial acid hydrolysis, methylation followed by methanolysis, IR spectroscopy, mass spectroscopy, etc. It was shown that capsicoside A2 is (25R)-5α-spirostan-3β-ol 3-O-β-D-galactopyranoside, capsicoside B2 is (25R)-5α-spirostan-3β-ol 3-O-[O-β-D-glucopyranosyl(1→4)-β-D-galactopyranoside], capsicoside A3 is (25R)-spirost-5-en-3β-ol 3-O-β-D-galactopyranoside, and capsicoside B3 is identical with funkioside C.

Search for Molluscicidal Agents: Saponins fromAgave cantalaLeaves

AbstractThree spirostanol glycosides, cantalasaponins 6-8, were isolated from the methanolic extract of the leaves of Agave cantala and were partially characterized. The purity of the compounds was established with the help of field desorption (FD)- and fast atom bombardment (FAB)-MS. This study has provided the first example of the co-occurrence of tigogenin and hecogenin glycosides with isomeric sugar chains. Cantalasaponin-7 displayed weak activity towards Biomphalaria glabrata, the snail vector of the parasitic disease schistosomiasis.

Spirostanol glycosides from Agave cantala

Two spirostanol glycosides, cantalasaponins -2 and -4 were isolated from the methanolic extract of the rhizomes of Agave cantala and were characterized. The first glycoside was found to be lethal against Biomphalaria glabrata, the snail vector of the disease schistosomiasis, at a concentration of 7 ppm.

Spirostanol glycosides from Asparagus plumosus

Three spirostanol glycosides were isolated from a methanol extract of the leaves of Asparagus plumosus and characterized.

Characterization of a minor compound, which accompanies the usual 22.ALPHA.(R)-O, 25.BETA.(S)-spirostanol glycoside, as a novel type of 22.BETA.(S)-O, 25.ALPHA.(S) analog.

The structure of one of the minor compounds, which coexists only with a 25β (S)-spirostanol glycoside (a steroid saponin) such as I, II, XI and XV, was determined to be the corresponding 22β (S)-0, 25α (S) analog Ia, IIa, XIa and XVa, respectively. Since it was believed that all the natural spirostanol glycosides have the 22α (R)-O configuration, these compounds are worthy of note as the first glycosides of 22β (S)-O-spirostanol so far isolated.

Co-occurrence and high-performance liquid chromatographic separation of the glycosides of rhodeasapogenin and its analogs which differ in the F-ring structure.

Two spirostanol glycosides (steroid saponins) R-3 (I) and R-8 (II), which were regarded, respectively, as pure 1-0-α-L-rhamnopyranosyl-(1-2)-β-D-xylopyranoside and 3-0-β-D-glucopyranoside of rhodeasapogenin (25S) (III), were shown by 13C-NMR to be accompanied by the corresponding glycosides of isorhodeasapogenin (25R) (IV) and convallamarogenin (Δ25 (27)) (V). Qualitative and preparative separation by HPLC of the components of I and II were studied and successfully achieved by a combination of two methods. They consisted equally of not three but four compounds, which were isolated in the pure state. Three of them were identified as the glycosides of III (major), IV and V, while the fourth was considered to have the same sugar moiety as I or II combined with a new aglycone different from III-V in the F-ring structure. The methods were applied also to some commonly known sterod saponins.

41 アグリコン部のF環構造のみを異にする数種のスピロスタノール配糖体の共存と,それらの高速液体クロマトグラフィーによる分離

41 アグリコン部のF環構造のみを異にする数種のスピロスタノール配糖体の共存と,それらの高速液体クロマトグラフィーによる分離

New Oligospirostanosides and Oligofurostanosides from Asparagus adscendens Roots

The methanol extract of the defatted roots of Asparagus adscendens Roxb. yielded beta-sitosterol beta-D-glucoside, two new spirostanol glycosides (asparanin C and asparanin D) and two new furostanol glycosides (asparoside C and asparoside D).

Tomatoside a from the seeds ofLycopersicum esculentum

Results are given which confirm the structure of the furostanol glycoside from tomato seeds forming wastes of the preserving industry. From a butanolic extract of the seeds ofLycopersicum esculentum Mill. we have isolated the furostanol glycoside tomatoside A (I) the structure of which has been established as 25(S)-5α-furostan-3β,22α,26-triol 26-O-β-D-glucopyranoside 3-O-[O-β-D-glucopyranosyl-(1→2)-O-β-D-glucopyranosyl-(1→4)-β-D-galactopyranoside]. At the same time, by enzymatic and chemical transformations three new spirostanol glycosides of neotigogenin have been obtained: tomatoside B (III), which is 25(S)-5α-spirostan-3β-ol 3-O-[O-β-D-glucopyranosyl-(1→2)-β-D-galactopyranoside], 25(S)-5α-spirostan-3β-ol 3-O-[O-β-D-glucopyranosyl-(1→4)-β-D-galactopyranoside] (V), and 25(S)-5α-spirostan-3β-ol 3-O-β-D-galactopyranoside (IV).

Mass spectra of spirostanol and furostanol glycosides

The electron impact mass spectra of twenty acetates and methylates of spirostanol and related furostanol glycosides of high molecular weight (above 650) have been investigated, and the most probable fragmentation patterns of the glycoside derivatives are presented. High resolution mass spectrometry provides useful information concerning the structures of both aglycone and sugar moieties as well as the molecular size of the oligoglycosides.

Diosgenin saponins from Dioscorea floribunda

Five spirostanol glycosides and two furostanol glycosides were isolated from Dioscorea floribunda. In addition to the IR spectra of the free glycosides and the MS of the peracetates and permethyl ethers, the most effective method for structural determination proved to be the NMR spectra of the free saponins in pyridine- d 5.