Triterpenoids from the leaves of far eastern species of the shrubby birchesBetula ovalifolia andB. middendorfii

From the unsaponifiable fraction of an ethereal extract of the leaves ofBetula ovalifolia have been isolated the new triterpene 20(S),24(R)-epoxydammarane-3,17,25-triol (V) and the corresponding monoketone at C³ (VI). The leaves ofB. middendorfii have yielded the triterpene (IX) and (X), identified as, respectively, dammar-23-ene-3,12,20(S),25-tetraol and damman-25-ene-3,12,20-(S),24-tetraol, which have been obtained previously from the leaves ofBetula platyphylla Sukatchev var.japonica.The species of birch were determined by V. I. Baranov of the Laboratory of Chemotaxonomy.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 323–329, May–June, 1981.     

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).     

Glycosylation of triterpenoids of the dammarane series. IX. β-D-glucopyranosides of 20(S),24(R)-epoxydammarane-3α,12β,17α,25-tetraol 25-tetraol

Glycosides have been synthesized from 20(S),24(R)-epoxy-dammarane-3α,12β,17α, 25-tetraol, which was isolated from the leaves ofBetula costata. Exhaustive glycosylation of betulafolienetetraol oxide with α-acetobromoglucose in the presence of mercury cyanide gave an acetylated 3,12,25-triglucoside (yield 61%), while glycosylation in the presence of insoluble silver compounds led to the formation of 3- and 12-mono- and 3,12- and 12,25-diglucopyranosides (total yield 57–82%). The structures of the glucosides obtained have been established on the basis of the results of IR and¹H and¹³C NMR spectroscopy.     

Triterpenoids from the leaves ofBetula lanata

From the unsaponifiable fraction of an ethereal extract of the leaves ofBetula lanata, in addition to 3-epiocotillol (I) we have isolated a new triterpene, 20(S), 24(R)-epoxydammarane-3α,11α,25-triol (V) and also derivatives of it — the monoacetates at C-3 (II) and C-11 (III), and the monoketone at C-3 (IV). The structures of compounds (I-V) have been established on the basis of the results of physicochemical investigations.     

Triterpene glycosides ofAstragalus and their genins. XLVIII. The structures of cycloalpigenin B and cycloalpioside B

The structures of the new cycloartane methylsteroid cycloalpigenin B and its glycoside cycloalpioside B, isolated fromAstragalus alopecurus Pall. (Leguminosae) have been determined on the basis of chemical transformations with the assistance of¹H and¹³C NMR spectroscopy and 2D NMR¹H-¹H and¹H-¹³C correlations of chemical signals and IR, CD, and electron-impact mass spectrometry. Cycloalpigenin B is 20R,24S-epoxycycloartane-3β,12α,16β,25-tetraol. A transition from cycloalpigenin B to cycloalpigenin A has been achieved. Cycloalpioside B is 20R,24S-epoxycycloartane-3β,12α,16β,25-tetraol 3-O-β-D-xylopyranoside.     

X-ray analysis of betulafolienetetraol oxide,a triterpene isolated from Betula costata trautv.

The structure of betulafolienetetraol oxide has been established by X-ray analysis as 20(S),24(R)-epoxydammar-3-α,12β,17α,25-tetraol.     

Triterpene glycosides of alfalfa VIII. Medinoside E from the leaves

From the leaves ofMedicago sativa L. (Leguminosae) we have isolated the glycoside soyasapogenol B — medinoside E. Medinoside E has the structure of olean-12-ene-3β,22β,24-triol 3-O-[O-α-L-rhamnopyranosyl-(1→2)-O-β-D-galactopyranosyl-(1→2)-O-β-D-glucopyranosyl-(1→2)-β-D-glucopyranuronoside].     

A new triterpene from the leaves ofBetula mandschurica

A new triterpene (I) has been isolated from the unsaponifiable fraction of an ethereal extract of the leaves ofBetula mandschurica to which, on the basis of the results of a physicochemical investigation and a comparison of the¹³C spectra with the spectra of known triterpenes — ocotillone (II) and 20(S)-hydroxydammar-24-en-3-one (III) — the structure of 20(S),24(S)-dihydroxydammar-25-3n-3-one has been assigned. An approach to the determination of the configuration of the asymmetric center at C₂₄ in 24-hydroxy derivatives of tetracyclic triterpenoids with an open side chain by the use of¹³C NMR spectroscopy is proposed.Pacific Ocean Institute of Bioorganic Chemistry of the Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 346–351, May–June, 1980.     

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.     

Two new dammarane-type triterpene sapogenins from Chinese red ginseng

Two new dammarane-type triterpene sapogenins were isolated from the Chinese red ginseng. The new sapogenins were named as 24,26-dihydroxy-panaxdiol (1) and 24-hydroxy-panaxdiol (2). Their structures were elucidated by the combined analysis of NMR and mass spectrometry as 20(S),25(R)-epoxydammarane-3β,12β,24β,26-tetraol (1) and 20(S),25-epoxydammarane-3β,12β,24α-triol (2). The complete signal assignments of the two compounds were carried out by 2D NMR spectral and NOE differential spectroscopy analysis.     

Triterpene glycosides of Astragalus and their genins XLIV. Structure of cyclocarposides A and C

The structures of two new cycloartane glycosides — cyclocarposides A and C, isolated from the herbAstragalus coluteocarpus Boiss. — have been established on the basis of spectral characteristics and chemical transformations. Cyclocarposides A and C are: 204R,24S-epoxycycloartane-3β,6α,17β,25-tetraol 3-O-(2-O-acetyl-β-D-xylopyranoside)6-O-(2-O-acetyl-α-L-rhamnopyranoside) and 20R,24S-epoxycyloartane-3β,6α,16β,25-tetraol 3-O-(2-O-acetyl-β-D-xylopyranoside) 6-O-α-L-rhamnopyranoside, respectively.     

Iriterpene glycosides of Astragalus and their genins XLIII. Cycloaraloside B from Astragalus amarus

The structure of a new cycloartane glycoside, cycloaraloside B, isolated from the roots ofAstragalus amarus Pall. (Leguminosae) has been established on the basis of chemical transformations and spectral characteristics: it is 20R,24S-epoxycycloartane-3β,6α,16β,25-tetraol 3-O-[O-α-L-rhamnopyranosyl-(1→2)-(6-O-acetyl-β-D-glucopyranoside)].     

Triterpene glycosides of Thalictrum squarrosum. III. Structures of squarrogenins 1 and 2

Two genins — squarrogenin 1 and squarrogenin 2 — have been isolated from nodding meadow rue by the hydrolysis of squarrosides A1 and A2. The compounds are epimeric at C-21 and have the following structures: 1 — (21R, 22S, 23R)-21-methoxy-21,23-epoxycycloart-24-ene-3β,22β-30-triol, C₃₁H₅₀O₅, mp 169–171°C (hexane-acetone), [α] ₅₄₆ ²⁰ ?11.06° (c 4.52; pyridine); and 2 — (21S, 22S, 23R)-21-methoxy-21,23-epoxycycloart-24-ene-3β,22β,30-triol, C₃₁H₅₀O₅, mp 190–193°C (hexane-acetone), [α] ₅₄₆ ²⁰ +106.6° (c 0.3; pyridine). The results of¹H and¹³C NMR spectroscopy and of mass spectrometry for the new compounds are given.     

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.     

Glycosylation of triterpenoids of the dammarane series. VII. Dammar-24-ene-3α,12β,17α,20(S)-tetraol β-D-glucopyranosides

Glucosides have been synthesized from dammar-24-ene-3,12,17,20(S)-tetraol (betulafolienetetraol), isolated from the leaves ofBetula pendula. Condensation with -acetobromoglucose in the presence of silver oxide and silicate has given acetylated betulafolienetetraol 3- and 12- mono- and 3,12- and 3,20-di-O--D-glucopyranosides, the total yield of which amounted to 75–80%. The structures of the semisynthetic glycosides have been established on the basis of the results of IR,¹H and¹³C NMR spectroscopy.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, USSR Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 225–229, March–April, 1988.     

Steroids of the spirostan and furostan series of plants of the Allium genus. XXIII. Structure of cepagenin and of alliospirosides C and D from Allium cepa

Two new steroid glycosides of the spirostan series have been isolated from the fruit ofAllium cepa L. (family Liliaceae): alliospirosides C and D. On the basis of chemical transformations and spectral characteristics it has been established that the aglycon of both glycosides is a new steroid sapogenin — cepagenin — having the structure of (24S,25R)-spirost-5-ene-1β,3β,24-triol. Alliospirosides C and D are cepagenin 1-O-[O-α-L-rhamnopyranosyl-(1→2)α-L-arabinopyranoside] and 1-O-[O-α-L-rhamnopyranosyl-(1→2)-O-β-D-galactopyranoside], respectively.     

Triterpenoids of the leaves of Betula pendula from different growth sites

A comparative study has been made of the triterpene fraction of the unsaponifiable part of ethereal extracts of five samples of the leaves ofBetula pendula collected in various regions of the Soviet Union. Together with known sterols and triterpenoids, two new compounds have been isolated — 12,20(S),25-trihydroxydammar-23-en-3-one and dammar-25-ene-3,12,17,20(S),24-pentaol, the structures of which have been determined on the basis of spectral characteristics and chemical transformations.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center of the Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 179–185, March–April, 1986.     

Steroid compounds of marine sponges. VII. Preparation of derivatives of sokotrasterol and halistanol sulfates and structure-activity interrelationships among these compounds

Five new sulfated derivatives of sokotrasterol and halistanol have been obtained: 24-nor-5α-cholane-2β,3α,6α,23-tetraol 2β,3α,6α-tri(sodium sulfate); 24-nor-5α-cholane-2β,3α,6α,23-tetraol 2β,3α,6α-tri(sodium sulfate) 23-palmitate; 24ε,25-dimethyl-5α-cholestane-2β,3α,6α-triol 3α-(sodium sulfate); 24ε,25-dimethyl-5α-cholestane-2β,3α,6α-triol 6α-(sodium sulfate); and 24ε,25-dimethyl-5α-cholestane-2β,3α,6α-triol 2β,6α-di(sodium sulfate). The inhibiting and membranolytic properties of the polysulfated steroids from sponges and their derivatives have been studied. It has been shown that physiological activity in this series of compounds depends on biphilicity.     

A new cycloartane triterpenoid from the leaves and stems of Fritillaria hupehensis

A new triterpenoid has been isolated from the leaves and stems of Fritillaria hupehensis Hsiao et K.C.Hsia.Its structure wasestablished as(23Z)-9,19-cycloart-23-ene-3α,25-diol 1 through chemical and spectroscopic studies including 2D NMR.Anotherknown triterpenoid 9,19-cycloart-25-ene-3β,24ξ-diol 2 was also isolated.     

A new steroid saponin from the leaves ofYucca aloifolia

A new steroid saponin has been isolated from the air-dry leaves ofYucca aloifolia L., and it has been shown to be (25R)-5β-spirostan-3β-ol O-D-glucopyranosyl-(1 → 2)-D-galactopyranoside. The substance melts at 302–303°C [α]D²⁰ ?27.2, (c 1.0; CHCl₃).