Triterpene glycosides and their genins fromThalictrum foetidum. I. The structure of foetoside C

A new glycoside — foetoside C — has been isolated from the epigeal part ofThalictrum foetidum L. and, on the basis of chemical transformations and spectral characteristics its structure has been established as oleanolic acid 28-[O-α-D-glycopyranosyl-(1 → 6)-O-β-D-glucopyranoside] 3-O-[O-β-D-xylopyranosyl-(1 → 3)-O-α-L-rhamnopyranosyl-(1 → 2)-α-L-arabinopyranoside].     

Steroid saponins and sapogenins ofAllium. XV. Eruboside B fromAllium erubescens

A new steroid glycoside of the spirostan series — eruboside B (I) — has been isolated from an ethanolic extract of the bulbs ofAllium erubescens C. Koh. In an acid hydrolysate, the aglycone β-chlorogenin (II) and the sugars D-glucose and D-galactose in a ratio of 3:1 have been found. By methylation, partial hydrolysis, and oxidation the structure of the spirostanol (I) has been established as (25R)-5α-spirostan-3β,6β-diol 3-O-{[O-β-D-glucopyranosyl-(1→3)]-[O-β-D-glucopyranosyl-(1→2)]-O-β-D-glucopyranosyl-(1→4)-β-D-galactopyranoside}.     

Steroid compounds of marine sponges. III. 24-Ethyl-25-methylcholesta-5,22-dien-3β-OL — A new marine sterol from the spongeHalichondria sp.

A new sterol — 24 ethyl-25-methylcholesta-5,22-dien-3β-ol — has been isolated by column chromatography on silica gel from extracts of the spongeHalichondria sp. Its structure has been established on the basis of an analysis of GLC-MS results and of PMR and¹³C NMR spectroscopy and has been confirmed by ozonolysis.     

Withasteroids ofPhysalis. V. A study of the1H and13C NMR spectra of the withasteroids visconolide and 28-hydroxywithaperuvin C

The PMR and¹³C NMR spectra of new withasteroids — visconolide and 28-hydroxywithaperuvin C, isolated fromPhysalis viscosa L. — have been investigated. A detailed analysis of the spectral characteristics obtained is given. For visconolide is proposed the structure of 4β,12α,17β,28-pentahydroxy-1-oxo-5β, 6β-epoxy-22R-witha-2,24-dienolide, and for 28-hydroxywithaperuvin C that of 6β,14α,17β,20R, 28-pentahydroxy-l-oxo-22R-witha-2, 4, 24-trienolide.     

Steroid saponins and sapogenins ofAllium. XVI. Turoside C fromAllium turcomanicum

From a methanolic extract of the bulbs ofAllium turcomanicum Rgl. we have isolated a new furostanol glycoside, turoside C (I). An acid hydrolysate was found to contain the aglycone — neoagigenin (II) — and the sugars D-xylose, D-glucose, and D-galactose in a ratio of 1:4:1. The structure of the furostanol (I) has been established by methylation, enzymatic hydrolysis, and oxidative cleavage, and also by the oxidative cleavage of (II), as (25S)-5α-furostan-2α,3β,6β,22α,26-pentaol 26-O-β-D-glucopyranoside 3-O-{[O-β-D-xylopyranosyl-(1→3)]-[O-β-D-glucopyranosyl-(1→2)-O-β-D-glucopyranosyl-(1→2)]-O-β-D-glucopyranosyl-(1→4)-β-D-galacto-pyranoside}.     

Triterpene saponins fromThalictrum minus. VII. Structure of thalicoside E

A new minor cycloartane glycoside — thalicoside E, 9,19-cyclo-20(S)-lanost-23-ene-3β,16β,22ζ,25,29-pentaol 3-O-β-D-galactoside 29-O-β-D-glucopyranoside — has been isolated from the epigeal part ofThalictrum minus L. (Ranunculaceae).     

Triterpene glycosides ofAstragalus and their genins. XXII. Cycloorbicoside A fromAstragalus orbiculatus

The quantitatively main glycoside — cycloorbicoside A — has been isolated from the epigeal parts of the plantAstragalus orbiculatus, and on the basis of chemical transformations and spectral characteristics its structure has been established as (23R,24S)-16β,23:16α,24-diepoxycycloartane-3β,7β,25-triol 3-0-β-D-xylopyranoside.     

Triterpene glycosides ofSilphium perfoliatum. III. Structure of silphioside E

A new triterpene glycoside — silphioside E — has been isolated from the epigeal part ofSilphium perfoliatum L. and its structure has been established on the basis of chemical transformations and spectral characteristics as oleanolic acid 28-0-β-D-glycopyranoside 3-0-[0-β-D-glycopyranosyl-(1 → 2)-β-D-glucopyranoside].     

Tripenoid glycosides of alfalfa. VII. Medicosides E and F

Two hederagenin glycosides — medicosides E and F — have been isolated from the roots ofMedicago sativa L. (Leguminosae). Medicoside E has the structure of hederagenin 28-O-β-D-glucopyranoside 3-O-[O-β-G-glucopyranosyl-(1→3)-β-D-xylopyranoside]. Medicoside F has the structure of hederagenin 28-O-β-D-glucopyranoside 3-O-[O-β-D-glucopyranosyl-(1→2)-α-L-arabinopyranoside].     

Glycosides of marine invertegrates. XI. Two new triterpene glycosides from holothurians of the familyStichopadidae

By repeated column chromatography on silica gel new glycosides have been isolated from the holothuriansAstichopus multifidus andStichopus chloronotus — astichoposide C and stichoposide C (I and II, respectively). Their structures have been studied with the aid of chemical and physicochemical methods. The complete structures of the glycosides have been established as 23(S)-acetoxy-3β-{4′-O-[O-(3-O-methyl-β-D-glucopyranosyl)-(1→3)-β-D-glucopyranosyl]-2′-O-[O-(3-O-methyl-β-D-glucopyranosyl)-(1→3)-O-β-D-xylopyranosyl-(1→4)-β-D-quinovopyranosyl]-β-D-xylopyranosyloxy}holosta-7,25-diene and -holost-7-ene.     

Coumarins ofHapolophyllum obtusifolium. Structures of two new coumarin glycosides

Two coumarin glycosides have been isolated from an aqueous ethanolic extract of the epigeal part ofHaplophyllum obtusifolium: (I) — C₁₆H₁₆O₁₀, mp 164–166°C, [α]_D ?52.4° (dimethylformamide); and (II) — C₂₆H₂₆O₁₂, mp 206–208°C, [α]_D ?110.5° (pyridine). It has been established on the basis of chemical transformations and spectral characteristics that (I) has the structure of fraxetin 7-O-β-D-glucopyranoside and (II) that of scopoletin 7-O-(6′-O-feruloyl-β-D-glucopyranoside).     

Onekotanogenin — A new triterpene genin from the holothurianPsolus fabricii

The structure of onekotanogenin — a new triterpene genin from the holothurianPsolus fabricii — has been established with the aid of¹H and¹³C NMR spectroscopy and a chemical correlation with the previously known cucumariogenin. Its structure has been determined as 20 (S)-acetoxy-3β, 16-dihydroxylanost-7-en-8-oic acid 18,16-lactone. It has been shown that its 25,26-dihydro derivative is the native genin of psolusoside B — a minor glycoside from the holothurianPsolus fabricii Düben et Koren.     

Triterpene saponins fromThalictrum minus. V. Structure of thalicoside B

The epigeal part ofThalictrum minus L. has yielded a new bidesmoside — thalicoside B — which has the structure of oleanolic acid 28-O-β-D-glucopyranoside 3-O-[O-α-L-rhamnopyranosyl-(1 → 2)-O-β-D-glucopyranosyl-(1 → 3)-α-L-arabinopyranoside].     

Acetylspectabiflaside fromStachys atherocalyx

From the herbage ofStachys atherocalyx C. Koch, a new flavonoid glycoside has been isolated — acetylspectabiflaside, with mp 237–242°C. On the basis of acetylation, the formation of a hydroxamic acid, alkaline, and enzymatic hydrolysis, and oxidative degradation, and also the results of UV, IR, and PMR spectroscopy, the structure of 4′,5,7,8-tetrahydroxy-3′-methoxyflavone 7-O-{acetyl-[O-β-D-glucopyranosyl-(1→2)-β-D-mannopyranoside]} has been proposed for acetylspectrabiflaside.     

Triterpene glycosides ofHedera helix II. Determination of the structure of glycoside L-6d from common ivy leaves

A new hederagenin pentaoside — glycoside L-6d — has been isolated from the leaves of common ivyHedera helix L., fam. Araliaceae, and its structure has been determined by using various NMR-spectroscopic methods. Glycoside L-6d is hederagenin 3-O-[O-α-L-rhamnopyranosyl-(1→4)-O-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosyl-(1→4)-O-α-L-rhamnopyranosyl-(1→2)-α-L-arabinopyranoside.     

Steroid glycosides ofNicotiana tabacum seeds I. The structures of nicotianosides A,B, and E

Two steroid glycosides of the spirostan series — nicotianosides A and B — and one glycoside of the furostan series — nicotianoside E — have been isolated from the seeds ofNicotiana tabacum L. Nicotianoside A is (25S)-5α-spirostan-3β-ol 3-O-β-D-glucopyranoside, nicotianoside B is (25S)-5β-spirostan-3β-ol 3-O-[O-α-L-rhamnopyranosyl-(1→2)-gb-D-glucopyranoside], and nicotianoside E is (25S)-5α-furostan-3β,22α,26-triol 26-O-β-glucopyranoside 3-O-[O-α-L-rhamnopyranosyl-(1→2)-β-D-glucopyranoside].     

Alkaloids of Aconitum kirinense. Structure of akirine

The known alkaloid lepenine and the new diterpene alkaloid akirine have been isolated from the epigeal part ofAconitum kirinense Nakai. To establish the structure of akirine, its spectral characteristics have been studied and an x-ray structural analysis has been made. It is 1α,8β-dihydroxy-16β-methoxy-9β,14β-methylenedioxy-3β,4β-epoxy-N-ethylaconitane — the first diterpene alkaloid with a lycoctonine skeleton containing a 9,14-methylenedioxy group and a β-oriented substituent at C14.     

Triterpene glycosides of Astragalus and their genins. XXIII. Cyclocanthogenin from Astragalus tragacantha

The epigeal part of the plantAstragalus tragantha Habl. (Leguminosea) has yielded (in addition to cyclosieversigenin, cyclocyclosiversioside F, and β-sitosterol β-D-glucopyranoside) a new methylsteroid of the cycloartane series — cyclocanthogenin — the structure of which has been established on the basis of chemical transformations and spectral characteristics, and also of a chemical correlation with the structure of cycloasgenin C, as 24S-cycloartane-3β,6α,16β,24,25-pentaol.     

Glycosides of marine invertebrates. XXVI. Holothurin A from the Pacific Ocean holothurianHolothvria squamifera. Isolation of the native aglycone

The known triterpene tetraoside holothurin A has been isolated from the Pacific Ocean holothurianHolothuria squamifera. By using two independent methods — enzymatic cleavage and two-stage Smith degradation — 22,25-epoxyholost-9(11)-ene-3β,12α,17α-triol, C₃₀H₄₆O₆, which is the native aglycone of holothurin A, was obtained. The structure of the native aglycone has been established on the basis of the results of IR, mass, and PMR spectroscopy.     

Phytoecdysteroids ofSilene nutans. III. Nusilsterone

A new ecdysteroid — nusilsterone — has been insolated from the whole plantSilene nutans L. It has been shown that it is 1β,2β,3β,14α,20R,22R,24ζ,25-octahydroxy-5-β-cholest-7-en-6-one.