[On steroidal sapogenins. III. Synthesis of 11-oxygenated spirostanes. (1)].
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Sapogenins↗
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Steroidal glycosides from Petunia hybrida L. seeds and their biological activity.
A new plant source containing steroidal glycosides of the furostane and spirostane series has been shown. Ten individual steroidal glycosides (petuniosides) of the spirostane and furostane series have been isolated from Petunia hybrida L. seeds. They differ in the structures of aglycone and oligosaccharide chain, four of them are novel compounds, and their chemical structures have been established. Petuniosides A, C, and E are 3-O-beta-D-galactopyranoside spirostane; 3-O-beta-D-glucopyranosyl (1-->4)-beta-D-galactopyranoside spirostane; and 3-O-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosyl (1-->4)-beta-D-galactopyranoside of (25R)-5 alpha-spirostan-3 beta-ol, respectively. Petuniosides B, D, and F are 3-O-beta-D-galactopyranoside spirostane; 3-O-beta-D-glucopyranosyl (1-->4)-beta-D-galactopyranoside spirostane; and 3-O-beta-D-glucopyranosyl(1-->2)-beta-D-glucopyranosyl (1-->4)-beta-D-galactopyranoside of (25R)-5 alpha-spirostane-2 alpha, 3 beta-diol, respectively. Petuniosides E and F are new compounds, and B, C, and D have been detected in the Petunia genus for the first time. Glycosides of the furostane series, petuniosides I and K, are derivatives of (25R)-5 alpha-spirostane-3 beta, 22 alpha, 26-triol, and K and M of (25R)-5 alpha-spirostane-2 alpha, 3 beta, 22 alpha, 26-tetraol. Petuniosides I and L are new compounds, and K and M are known, but have been detected in the Petunia genus for the first time. Growth-stimulating activity has been established for petunioside M. This glycoside has been shown to enhance cucumber resistance to cucumber green eye-sport mosaic virus.
Carbohydrate Sequence↗
13C cross-polarization MAS NMR study of some steroidal sapogenins.
Cross-polarization (CP) magic angle spinning (MAS) solid-state 13C NMR spectra of five steroidal sapogenins: tigogenin ((25R)-5alpha-spirostan-3beta-ol), hecogenin (3beta-hydroxy-(25R)-5alpha-spirostan-12-one), diosgenin ((delta5-(25R)-5alpha-spirosten-3beta-ol), sarsasapogenin ((25S)-55beta-spirostan-3beta-ol), and smilagenin ((25R)-5beta-spirostan-3beta-ol) were recorded. The solid-state chemical shifts are almost the same as for solution, which indicate that confirmations of sapogenins are similar in both phases. The doubling of some resonances in the spectra of solid diosgenin shows that there are two molecules in the crystallographic asymmetric unit. The cross-polarization time constants T(CP) and relaxation times in the rotating frame T(1rho)H were obtained from the variable-contact cross-polarization experiments for tigogenin and diosgenin. The values of T(CH) for methyl carbons indicate fast rotation of methyl groups and are close (0.30-0.35 ms), suggesting that the interaction with their intramolecular neighbors is similar. The values of T(1rho)H for carbons of tigogenin are longer than of diosgenin. Very efficient cross-polarization dynamics results in short time required for obtaining a spectrum of sapogenin of remarkably good quality.
Carbon Isotopes↗
Steroidal saponins from fruits of Tribulus terrestris.
Further studies on the constituents of the fruits of Tribulus terrestris led to the isolation of five new steroidal saponins (terrestrosin A-E), (25R,S)-5 alpha-spirostan-3 beta-ol-3 -O-beta-D-galactopyranosyl(1-2)-beta-D- glucopyranosyl(1-4)-beta-D-galactopyranoside, (25R,S)-5 alpha-spirostan-3 beta-ol-3-O-beta-D-glucopyranosyl(1-4)-[alpha-L- rhamnopyranosyl(1-2)]-beta-D-galactopyranoside, (25R,S)-5 alpha-spirostan-12-on-3 beta-ol-3-O-beta-D-galactopyranosyl (1-2)-beta-D-glucopyranosyl(1-4)-beta-D-galactopyranoside, hecogenin 3-O-beta-D-galactopyranosyl)1-2)-[beta-D- xylopyranosyl(1-3)]-beta-D-glucopyranosyl(1-4)-beta-D-galactopyranoside and (25R,S)-5 alpha-spirostane-2 alpha, 3 beta-diol-3- O-beta-D-galactopyranosyl(1-2)-beta-D-glucopyranosyl(1-4)-beta-D- galactopyranoside, together with five known steroidal saponins, desgalactotigonin, F-gitonin, desglucolanatigonin, gitonin and tigogenin 3-O-beta-D- xylopyranosyl)1-2)-[beta-D-xylopyranosyl)1-3)]-beta-D-glucopyranosyl)1-4 )- [alpha-L-rhamnopyranosyl(1-2)]-beta-D-galactopyranoside. The structures of the new saponins were elucidated on the basis of spectroscopic analyses, including two-dimensional NMR techniques, and chemical reactions.
Chromatography, High Pressure Liquid↗
Steroidal saponins from roots of Asparagus officinalis.
Sarsasapogenin M (1) and sarsasapogenin N (2), two new oligospirostanosides with a unique aglycone moiety, (25S)-5beta-spirostan-3beta, 17alpha-diol, along with seven known compounds (25S)-5beta-spirostan-3beta-ol-3-O-beta-d-glucopyranosyl-(1,2)-[beta-d-xylopyranosyl-(1,4)]-beta-d-glucopyranoside (3), (25S)-5beta-spirostan-3beta-ol-3-O-beta-d-glucopyranosyl-(1,2)-beta-d-glucopyranoside (4), (25S)-5beta-spirostan-3beta-ol-3-O-alpha-l-rhamnopyranosyl-(1,2)-[alpha-l-rhamnopyranosyl-(1,4)]-beta-d-glucopyranoside (5), (25S)26-O-beta-d-glucopyranosyl-5beta-furost-20 (22)-ene-3beta,26-diol-3-O-beta-d-glucopyranosyl-(1,2)-beta-d-glucopyranoside (6), yamogenin (7), beta-sitosterol (8), and sitosterol-beta-d-glucoside (9) were isolated from the roots of Asparagus officinalis L. Their structures were determined by spectral analysis, including extensive 1D and 2D NMR experiments.
Asparagus Plant↗
New spirostanol saponins from Chinese chives (Allium tuberosum).
Three new spirostanol saponins have been isolated from the seeds of Allium tuberosum. On the basis of acid hydrolysis and comprehensive spectroscopic analysis, their structures were established as tuberoside J, (25R)-5alpha-spirostan-2alpha,3beta,27-triol 3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranoside; tuberoside K, (25R)-5alpha-spirostan-2alpha,3beta,27-triol 3-O-alpha-L-rhamnopyranosyl-(1-->2)-[alpha-L-rhamnopyranosyl-(1-->4)]-beta-D-glucopyranoside; and tuberoside L, 27-O-beta-D-glucopyranosyl-(25R)-5alpha-spirostan-2alpha,3beta,27-triol 3-O-alpha-D-rhamnopyranosyl-(1-->2)-[alpha-L-rhamnopyranosyl-(1-->4)]-beta-D-glucopyranoside.
Allium↗
Steroidal saponins from the bulbs of Camassia cusickii.
Six new steroidal saponins have been isolated from the fresh bulbs of Camassia cusickii. Their structures were determined by spectroscopic analysis and some chemical transformations to be (25R)-5 alpha-spirostan-3 beta,6 alpha-diol (chlorogenin) 6-O-beta-D-glucopyranoside, chlorogenin 6-O-beta-D-glucopyranosyl-(1----2)-beta-D-glucopyranoside, chlorogenin 6-O-beta-D-glucopyranosyl-(1----3)-beta-D-glucopyranoside, chlorogenin 6-O-beta-D-glucopyranosyl-(1----2)-O-[beta-D-glucopyranosyl-(1----3)]-beta- D-glucopyranoside, (25R)-6 alpha-hydroxy-5 alpha-spirostan-3-one 6-O-beta-D-glucopyranosyl- (1----3)-beta-D-glucopyranoside and (25R)-3,3-dimethoxy-5 alpha-spirostan-6 alpha-ol 6-O-beta-D-glucopyranosyl-(1----3)-beta-D-glucopyranoside. The saponins isolated were shown to contribute to the bitter taste of the bulbs.
Carbohydrate Sequence↗
12-Hydroxy steroidal glycosides from the caudex of Yucca gloriosa.
The structures of the new steroidal saponins (tentatively named YS-XI, -XII and -XIII) have been isolated from the caudex of Yucca gloriosa and characterized as 3-O-beta-D-glucopyranosyl-(1----2)-beta-D-galactopyranosyl 5 beta- (25R)-spirostan-3 beta, 12 beta-diol, 3-O-beta-D-glucopyranosyl-(1----2)- [beta-D-glucopyranosyl-(1----3)]-beta-D-glucopyranosyl 5 beta- (25R)-spirostan-3 beta, 12 beta-diol and 3-O-beta-D-glucopyranosyl-(1----2)- beta-D-galactopyranosyl 5 beta-(25R)-spirostan-2 beta,3 beta,12 beta-triol, respectively.
Acetylation↗
Steroidal saponins from the rhizomes of Smilax sieboldii.
Six new steroidal saponins were isolated from the rhizomes of Smilax sieboldii. Their structures were determined by spectroscopic analysis and hydrolysis to be 3 beta-hydroxy-(25R)-5 alpha-spirostan-6-one (laxogenin) 3-O-beta-D-glucopyranosyl-(1----4)-O-[alpha-L-arabinopyranosyl-(1- ---6)]-beta-D-glucopyranoside, laxogenin 3-O-alpha-L-arabinopyranosyl-(1----6)-beta-D-glucopyranoside, 3 beta,27-dihydroxy-(25S)-5 alpha-spirostan-6-one 3-O-beta-D-glucopyranosyl-(1----4)-O-[alpha-L-arabinopyranosyl-(1- ---6)]- beta-D-glucopyranoside, 26-O-beta-D-glucopyranosyl-3 beta,22 xi,26-trihydroxy-(25R)-5 alpha-furostan-6-one 3-O-alpha-L-arabinopyranosyl-(1----6)-beta-D-glucopyranoside, 26-O-beta-D-glucopyranosyl-3 beta,22 xi,26-trihydroxy-(25R)-5 alpha-furostan-6- one 3-O-beta-D-glucopyranosyl-(1----4)-O-[alpha-L-arabinopyranosyl-(1- ---6)]- beta-D-glucopyranoside and (25R)-5 alpha-spirostan-3 beta-ol (tigogenin) 3-O-beta-D-glucopyranosyl-(1----4)-O-[alpha-L-arabinopyranosyl- (1----6)]-beta-D-glucopyranoside. The inhibition of cAMP phosphodiesterase by the saponins was evaluated.
3',5'-Cyclic-AMP Phosphodiesterases↗
Steroidal saponins from the fruits of Asparagus racemosus.
Three steroidal saponins, racemosides A (1), B (2) and C (3), were isolated from the methanolic extract of the fruits of Asparagus racemosus, and characterized as (25S)-5beta-spirostan-3beta-ol-3-O-{beta-D- glucopyranosyl (1-->6)-[alpha-L-rhamnopyranosyl (1-->6)-beta-D-glucopyranosyl (1-->4)]-beta-D-glucopyranoside}, (25S)-5beta-spirostan-3beta-ol-3-O-alpha-L-rhamnopyranosyl (1-->6)-beta-D-glucopyranosyl (1-->6)-beta-D-glucopyranoside and (25S)-5beta-spirostan-3beta-ol-3-O-{alpha-L-rhamnopyranosyl-(1-->6)-[alpha-L-rhamnopyranosyl (1-->4)]-beta-D-glucopyranoside}, respectively, by spectrometric analysis and some chemical strategies.
Asparagus Plant↗
Steroidal saponins from the bulbs of Allium schubertii.
Phytochemical examination of the fresh bulbs of Allium schubertii led to the isolation of four new steroidal saponins together with a known saponin. The structures of the new saponins were established by spectroscopic data, hydrolysis and chemical correlation as (25R and S)-5 alpha-spirostan-2 alpha,3 beta,6 beta-triol 3-O-beta-D-glucopyranosyl-(1-->2)-O-[4-O-benzoyl-beta-D-xylopyranosyl- (1-->3)]-O-beta-D-glucopyranosyl-(1-->4)-beta-D-galactopyranoside, (25R and S)-5 alpha-spirostan-2 alpha,3 beta,6 beta-triol 3-O-beta-D-glucopyranosyl-(1-->2)-O-[3-O-benzoyl-beta-D-xylopyranosyl- (1-->3)]-O-beta-D-glucopyranosyl-(1-->4)-beta-D-galactopyranoside, (25R and S)-5 alpha-spirostan-2 alpha,3 beta,6 beta-triol 3-O-beta-D-glucopyranosyl-(1-->2)-O-[4-O-(3S)-3-hydroxy-3-methylgluta royl- beta-D-xylopyranosyl-(1-->3)]-O-beta-D-glucopyranosyl-(1-->4)-beta-D- galactopyranoside and 26-O-beta-D-glucopyranosyl-(25R and S)-5 alpha-furostan-2 alpha,3 beta,6 beta,22 zeta,26-pentol 3-O-beta-D-glucopyranosyl-(1-->2)-O-[beta-D-xylopyranosyl-(1-->3)]-O-bet a- D-glucopyranosyl-(1-->4)-beta-D-galactopyranoside, respectively.
Allium↗
Structures of toxic steroidal saponins from Narthecium asiaticum MAXIM.
The full structures of the two steroidal saponins from Narthecium asiaticum MAXIM. We previously identified as toxic substances by monitoring the toxicity in guinea pigs were phytochemically reinvestigation on the aerial parts of the plant. The desired toxic saponins (6,7) were isolated together with two known lignan glucosides (1,2), a known flavonoid glucoside (3), a new furanone glucoside (4), a known steroidal saponin (5) and a new steroidal saponin (8). The structures of the new furanone glucoside, toxic saponins and new saponin were determined on the basis of spectroscopic data and acid- or enzymatic-catalyzed hydrolysis to be (S)-5-beta-D-glucopyranosyloxy-4-methoxyfuran-2(5H)-one (4), (25R,S)-5 beta-spirostan-3 beta-ol 3-O-[O-beta-D-glucopyranosyl-(1-->2)-] O-[alpha-L-arabinopyranosyl-(1-->3)]-beta-D-galactopyranoside] (6), (25R,S)-5 beta-spirostan-3 beta-ol 3-}O[O-beta-D-glucopyranosyl-(1-->2- O-[beta-D-xylopyranosyl-(1-->3)]-beta-D-galactopyranoside] (7) and (24S,25R)-5 beta-spirostan-3 beta,24-diol 3-O-[O-beta-D- glucopyranosyl-(1-->2)-O-]alpha-L-arabinopyranosyl-(1-->3)]-beta-D - galactopyranoside] (8), respectively.
Carbohydrate Sequence↗
[Structural elucidation of the anticoagulation and anticancer constituents from Allium chinense].
Six compounds were isolated from the anticoagulation and anticancer fractions of the bulbs of Allium chinense G. Don. On the basis of chemical evidence and spectral analysis (IR, EI-MS, 1HNMR, 13CNMR, 1H-1H COSY, HMBC, HMQC and NOESY), their structures were established as (25R, S)-5 alpha-spirostane-3 beta-ol 3-O-(beta-D-glucopyranosyl-(1-->2)-[beta-D-glucopyranosyl-(1-->3)]-beta-D- glucopyranosyl-(1-->4)-beta-D-galactopyranoside) (1), (25R, S)-5 alpha-spirostane-3 beta-ol 3-O-(beta-D-glucopyranosyl (1-->2)-[beta-D-glucopyranosyl-(1-->3)](6-acetyl-beta-D-glucopyranosyl)- (1-->4)-beta-D-galactopyranoside) (2), (25R, S)-5 alpha-spirostane-2 alpha, 3 beta-diol 3-O-(beta-D-glucopyranosyl-(1-->2)-O-beta-D-glucopyranosyl-(1-->4)-beta-D- galactopyranoside) (3), (25S)-24-O-beta-D-glucopyranosyl-3 beta, 24 beta-dihydroxy-5 alpha-spirost-3-O-alpha-arabinopyranosyl-(1-->6)-beta-D-glucopyranoside (4), chinenoside II (5) and 2,3,4,9-tetrahydro-1-methyl-1H-pyrido [3,4-b] indole-3-carboxylic acid (6). 4 is a new steroidal saponin, named chinenoside VI. Compounds 1 to 3 are three pairs of steroidal saponin epimers. Among them, the 25S epimer of 2 is first reported, the 25R epimer of 2 and compound 6 were isolated from this title plant for the first time. The relative configuration of compound 6 was firstly determined by NOESY spectrum, and signals of C, H were assigned definitely.
Allium↗
[A new steroidal glycoside from fermented leaves of Agave americana].
OBJECTIVE: To investigate the constituents of fermented leaves of Agave americana, and discover new compounds. METHOD: Compounds were purified with silica gel and C8 reverse--phase silica gel column chromatography. The structures were elucidated by chemical and spectroscopic evidence. RESULT: Three steroidal compounds were obtained and their structures were identified as (25R)-5 alpha-spirostan-3 beta, 6 alpha, 23 alpha-triol 6-O-beta-D-glucopyranoside(1), (25R)-5 alpha-spirostan-3 beta, 6 alpha, 23 alpha-triol-3, 6-di-O-beta-D-glucopyranoside (cantalasaponin-1) (2) and (25R)-5 alpha-spirostan-3 beta, 6 alpha, 23 alpha-triol(hongguanggenin) (3). CONCLUSION: Compound 1 is new compound, named agamenoside C.
Agave↗
Steroidal glycosides from Agave cantala.
Two new steroidal glycosides, agaveside A and B, isolated from the fruits of Agave cantala were characterized as 3 beta-O-[beta-D-xylopyranosyl-(1----2),beta-D-xylopyranosyl-(1----3), beta-D-glucopyranosyl-(1----3)-[beta-D-xylopyranosyl-(1----3)-beta-D- galactopyranosyl-(1----2)]-beta-D-glucopyranosyl]-(25R)-5 alpha-spirostane and 3 beta-O-[beta-D-xylopyranosyl-(1----2), beta-D-xylopyranosyl-(1----3)-beta-D-glucopyranosyl-(1----3)- [beta-D-galactopyranosyl-(1----2)]-beta-D-glucopyranosyl]-(25R)-5 alpha-spirostane. The structures were elucidated by a combination of 13CNMR spectroscopy, chemical degradation and fast atom bombardment mass spectrometry.
Carbohydrate Conformation↗
Oligofurostanosides from Asparagus curillus leaves.
The methanol extracted leaves of Asparagus curillus furnished two oligospirostanosides (curillins G and H) and two oligofurostanosides (curillosides G and H) which were characterized as 3-O-[beta-D-glucopyranosyl(1-->4)-beta-D-glucopyranosyl]-(25S)-5 beta- spirostan-3 beta-ol; 3-O-[(alpha-L-rhamnopyranosyl(1-->2))(-beta-D-glucopyranosyl(1--> 4))-beta-D-glucopyranosyl]-(25S)-5 beta, spirostan-,3 beta-ol; 3-O-[(alpha-L-rhamnopyranosyl(1-->2)) (beta-D-glucopyranosyl(1-->4))-beta-D-glucopyranosyl]-26-O-[beta-D- glucopyranosyl]-22 alpha-methoxy-(25S)-5 beta-furostan-3 beta,26-diol and 3-O-[(alpha-L-rhamnopyranosyl(1-->2))-(beta-D-glucopyranosyl(1-->4))- beta-D-glucopyranosyl]-26-O-[beta-D-glucopyranosyl]-(25S)-5 beta-furostan-3 beta,22 alpha,26-triol, respectively.
Carbohydrate Sequence↗
Differential behavior of (25R)-5,6-epoxyspirostan-22 alpha-O-3 beta-ol and (25R)-5,6-epoxyspirostan-22 alpha-O-3 beta, 4 beta-diol toward Dowex.
The acid-catalyzed hydrolytic cleavage of the 5,6-epoxyspirostane derivatives by the cation exchange resin Dowex 50W X8 has been exploited with the goal of developing synthetic protocols toward 3,4,5,6-polyhydroxyspirostane analogs that can serve as intermediates to potential biologically active compounds. Whereas the diastereomers (25R)-5 alpha, 6 alpha-epoxyspirostan-22 alpha-O-3 beta-ol and (25R)-5 beta, 6 beta-epoxyspirostan-22 alpha-O-3 beta-ol yield two products, (25R)-6 beta-methoxyspirostan-22 alpha-O-3 beta, 5 alpha-diol and (25R)-spirostan-22 alpha-O-3 beta, 5 alpha, 6 beta-triol on Dowex treatment in water-methanol, the alpha- and beta-diastereomers of the 5,6-epoxy derivative of 3 beta, 4 beta-diol provide a single product, (25R)-3 beta, 6 beta-dihydroxy-5 alpha-spirostan-4-one, in good yields. The structures of these products have been confirmed using 1H NMR, 13C NMR, and 1H-1H J-correlated spectroscopies. Multifunctional product formation suggests tremendous utility of Dowex in steroid synthesis. The product formation has been rationalized on the basis of differential conformational constraints of the A/B rings of the different epoxides in directing the reaction course. The reaction shows an interesting example of stereoelectronic effect of a single hydroxy group in discriminating solvent participation.
Anion Exchange Resins↗
Novel 5beta-hydroxyspirostan-6-ones ecdysteroid antagonists: synthesis and biological testing.
Eight new 5beta-hydroxy-spirostan-6-ones bearing hydroxy and amino functions in the A ring, i.e., 3beta-OH, 3alpha-OH, 2beta,3beta-OH, 2alpha,3beta-OH, 3beta-NH2, 2alpha-NH2-3beta-OH, 2beta-NH2-3beta-OH, and 2beta-OH-3beta-NH2, were efficiently synthesized, and their antiecdysteroid activities were evaluated on the metamorphosis bioassay of mosquito Aedes aegypti. To our knowledge, these new steroids represent the first 5beta-hydroxy-spirostanes which have been tested for antiecdysteroid activity in mosquitoes. The higher antagonistic effect was found for compounds bearing the 3beta-hydroxy and 2beta,3beta-dihydroxy functionality, which show promise as environmental friendly insecticides.
Aedes↗