Withasteroids of Physalis. IX. Physangulide — The first natural 22S-withasteroid

A new withasteroid — physangulide — has been isolated from the leaves ofPhysalis angulata L. It has been shown that physangulide is the first natural 22S-withanolide. Its structure has been determined as 3β,4β,20,24,25-pentahydroxy-1-oxo-5β,6β-epoxy-20R,22S,24S,25R-withanolide. Its¹H and¹³C NMR spectra, confirming this interpretation, are given. Institute of the Chemistry of Plant Substances, Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 366–371, May–June, 1990.     

Triterpene glycosides of Astragalus and their genins XXXIX. Cycloaraloside D from Astragalus amarus

The structure of a triterpene glycoside of the cycloartane series — cycloaraloside D, isolated from the roots ofAstragalus amarus Pall. (Leguminosae) — has been established on the basis of chemical transformations and spectral characteristics. Cycloaraloside D is 20R, 24S-epoxycycloartane-3β, 6α, 16β, 25-tetraol 3-0-[0-α-L-rhamnopyranosyl-(1 → 2)-β-D-glucopyranoside]. Institute of Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 526–528, July–August, 1991.     

Synthesis of 24-ethylcholesta-7, 22E-diene-3β, 5β-triol — A natural trihydroxysteroid from the bryozoan Myriapora truncata

24-Ethylcholesta-7, 22E-diene-3β,5α,6β-triol — a natural trihydroxysteroid from the bryozoanMyriapora truncata — has been synthesized from stigmasterol. Institute of Bioorganic Chemistry, Academy of Sciences of the Belorussian SSR, Minsk. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 664–669, September–October, 1989.     

Phytoecdysteroids of Rhaponticum carthamoides. II. Rhapisterone B

A new ecdysteroid (rhapisterone B) has been isolated from the seeds ofRhaponticum cathamoides (Willd.) Iljin. (familyCompositae). It has been shown that it is 2β, 3β, 11α, 14α, 20R, 24ξ-hexahydroxy-5β-cholest-7-en-6-one. Institute of the Chemistry of Plant Substances, Uzbek Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 806–808, November–December, 1991.     

Leuconine — A new alkaloid from Aconitum leucostomum and A. septentrionale

A new alkaloid — leuconine — has been isolated from the epigeal parts ofAconitum leucostomum andA. septentrionale, and its structure has been established on the basis of spectral characteristics. Institute of Chemistry of Plant Substances, Uzbekistan Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 538–540, September–October, 1992.     

Triterpene glycosides of Thalictrum squarrosum. IV. Structures of squarrosides A1, A2, B1, and B2

Four new cycloartane glycosides have been isolated from a methanolic extract ofThalictrum squarrosum Stephan ex Willd.: squarroside A1 (I) — (21R, 22S, 23R)-3β-(β-D-glucopyranosyloxy)-21α-methoxy-21,23-epoxycycloart-24-ene-22β,30-diol, C₃₀H₆₀O₁₀; squarroside A2 (II) — the (21S)-epimer of compound (I); squarroside B1 (III) (21R, 22S, 23R)-3gb-[O-α-L-rhamnopyranosyl-(1 → 6)-β-D-glucopyranosyloxy]-21α-methoxy-21,23-epoxycycloart-24-ene-22β,30-diol, C₄₃H₇₀O₁₄; and squarroside B2 (IV) — the (21S)-epimer of compound (III). The proposed structures were determined on the basis of¹H and¹³C NMR spectroscopy, FAB mass spectrometry, and chemical transformations. Irkutsk Institute of Organic Chemistry, Siberian Branch, USSR Academy of Sciences. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 516–523, July–August, 1989.     

Insect phermones and their analogues XXXVIII. Synthesis of (±)-3-methylheneicosan-2-one and (±)-2-acetoxy-3,7-dimethylpentadecane using the reductive β-vinylation of α-olefins

Schemes are proposed for the synthesis of (±)-3-methylheneicosan-2-one and (±)-2-acetoxy-3,7-dimethylpentadecane — racemic analogues of the sex pheromones of the common cockroach (Blatella germanica) and of plane sawflies of the generaDiprion andNeodiprion, respectively, using the reductive β-vinylation of α-olefins. Institute of Chemistry of the Bashkir Scientific Center, Urals Division of the Russian Academy of Sciences, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 567–571, September–October, 1992.     

Steroids of the spirostan and furostan series from plants of the genus Allium. XXVI. Structure of anzurogenin and anzuroside from the collective fruits of Allium suvorovii and Allium stipitatum

A new steroid glycoside of the spirostan series, anzuroside, has been isolated from the collective fruits of the cocultivatedAllium suvorovii Rgl. andA. stipitatum Rgl. (family Liliaceae, local name “anzur”). Enzymatic cleavage of the glycoside has given the previously undescribed steroid sapogenin anzurogenic C, which has the structure of (24S, 25S)-2α,3β,5,24-tetrahydroxy-5β-spirostan-6-one. Anzuroside is the 24-O-β-D-glucopyranoside of anzurogenin C. Institute of the Chemistry of Plant Substances, Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 505–510, July–August, 1989.     

Triterpene glycosides of Astragalus and their genins XXXV. Cycloaraloside C from Astragalus amarus

A new triterpene glycoside of the cycloartane series (cycloaraloside C) has been isolated from the roots of the plantAstragalus amarus Pall. (Leguminosae). Cycloaraloside C is a bioside of cyclosieversigenin including one D-glucose residue and one D-apiose residue. The structure of the glycoside has been shown on the basis of the chemical transformations and spectral characteristics as 20R,24S-epoxycycloartane-3β,6α,16β,25-tetraol 3-O-[O-(D-apio-β-D-furanosyl)-(1 → 2)-β-D-glucopyranoside]. This is the first time that D-apiose has been found among cycloartane glycosides. Institute of Chemistry of Plant Substances, Academy of Sciences of the Uzbek, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 783–787, November–December, 1990.     

Secondary metabolites of Ulocladium chartarum. Ulocladols A and B — New phytotoxins of terpenoid nature

Ulocladols A and B — new exometabolites having a mixed sesquiterpenoid-polyketide nature that are structurally close to the host-specific toxins ofAlternaria citri — have been isolated from the deuteromyceteUlocladium chartarum. Both substances inhibit the growth of cotton seeds. All-Union Scientific Research Institute of Phytopathology, Moscow Province, Golitsyno. M. V. Lomonosov Moscow State University. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 642–648, September–October, 1991.     

Phytoecdysteroids of the plants of the genusSilene XV. Silenoside F — Brahuisterone 3-O-β-D-glucopyranoside fromSilene brahuica

A new brahuisterone glycoside — silenoside F — has been isolated from the epigeal part ofSilene brahuica Bois. (fam. Caryophyllaceae). Its structure has been established by an analysis of spectral characteristics: 3β,5,14α,22R,25-pentahydroxy-5β-cholest-6-one 3-O-β-D-glucopyranoside. Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan, Tashkent, fax (3712) 89 14 75. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 734–737, November–December, 1994.     

Triterpene glycosides of Astragalus and their genins XXXII. Cyclocarposide from Astragalus coluteocarpus

A new triterpene glycoside of the cycloartane series, which has been called cyclocarposide, has been isolated from the epigeal part of the plantAstragalus coluteocarpus Boiss. (Leguminosae). The structure of cyclocarposide has been established on the basis of chemical transformations and spectral characteristics as 20R,24S-epoxycycloartane-3β,6α,16β,25-tetraol 6-0-α-L-rhamnopyranoside 3-0-α-D-xylopyranoside. Institute of Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Pamir Biological Institute, Academy of Sciences of the Tadzhik SSR, Khorog. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 653–656, September–October, 1990.     

Steroids of the spirostan and furostan series from nolina microcarpa III. Structure of nolinofurosides G and H

Two new glycosides which have been called nolinofurosides G(I) and H(III), have been isolated from the leaves ofNolina microcarpa. Nolinofuroside G is the sodium salt of 26-β-D-glucofuranosyloxy-(25S)-furost-5,20(22)-diene-1β, 3β-diol 1-sulfate, and nolinofuroside H is the sodium salt of 1-β-D-fucopyranosyloxy-26-β-D-glucopyranosyloxy-(25S)-furost-5,20(22)-dinen-1β-3β-ol 3-sulfate. M. V. Frunze Simferopol' State University. Institute of the Chemistry of Plant Substances, Uzbek. Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 801–806, November–December, 1991.     

Insect pheromones and their analogues XLIII. Chiral pheromones from (S)-(+)-3,7-dimethylocta-1,6-diene 3. Synthesis of (4R)-4-methylnonan-1-OL — Sex pheromone of Tenebrio molitor and its racemic analogue

Starting from the readily available enantiomerically enriched (S)-(+)-3,7-dimethylocta-1,6-diene (ee ≃ 50%), we have synthesized (4R)-4-methylnonan-1-ol — the sex pheromone of the yellow mealworm bettleTenebrio molitor L. A scheme for synthesizing the racemic analogue of the pheromone from 4-methyltetrahydropyran has been developed. Institute of Organic Chemistry, Urals Branch, Russian Academy of Sciences. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 711–714, November–December, 1992.     

Insect pheromones and their analogues XLII. Synthesis of 2,6-dimethyloct-1-yl formate — A mimic of the aggregation pheromone of flour beetles

2-6-Dimethyloctan-1-ol, the formate of which is a mimic of the aggregation pheromone of the flour beetlesTribolium confusum andT. castaneum, has been synthesized by the hydroboration of 2,6-diemthyloct-1-ene, obtained from β-methylvaleric acid. Institute of Organic Chemistry, Urals Branch, Russian Academy of Sciences, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 571–573, September–October, 1992.     

α- and β-scopodonnines from Datura inoxia seeds

A mixture of two alkaloids, d, ℓ-α- and β-scopodonnines, known earlier as synthetic products, has been isolated for the first time from the seed ofDatura inoxia. The spatial structure of β-scopodonnine dimethiodide has been established by the x-ray structural method. Institute of Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 532–537, July–August, 1991.     

Lignans of the bark of Syringa volgaris

Two lignans have been isolated from the bark ofSyringa vulgaris and identified: (+)-lariciresinol 4-β-D-glucopyranoside (I) and -olivil 4-β-D-glucopyranoside (II). This is the first time that glycoside (9) has been described. All-Union Scientific-Research Institute of Medicinal Plants Scientific-Production Association, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 768–771, November–December, 1991.     

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.     

Cembrenolides of a soft coral Lobophytum sp. (coelenterata,octocorallia, alcyonacea)

The known cembrenolide sarcophin and its new acetoxy derivative — 13-acetoxy-7,8-epoxycembra-1(15),3,11-trien-2,16-olide — have been isolated from the soft coralLobophytum sp.. The compounds isolated are inhibitors of the activity of Na⁺K⁺-ATPase and are membranotropic agents. The structures of the compounds have been shown on the basis of the results of NMR spectroscopy. Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 762–765, November–December, 1990.     

Withasteroids of Physalis. X. Circular dichroism of withasteroids from plants of the genus Physalis

The circular dichroism method has been used to establish the stereochemical features of the structure of the withasteroids. The 22S-configuration of the asymmetric center has been confirmed for physangulide. The 22R-configuration has been confirmed for 14α-hydroxyixocarpanolide, vamonolide, ixocarpanolide, 24,25-epoxywithanolide D, and withanolide T. On the basis of changes in the circular dichroism spectra in acid and alkaline media it is suggested that in compounds having a 4β-hydroxy-1-oxo-5β,6β-epoxy-2,3-ene grouping the Δ^2,3 bond disappears, while in compounds having a 5α-hydroxy-1-oxo-6α,7α-epoxy-2,3-ene grouping dehydration takes place at C-4-C-5. These characteristics can be used in the identification of the withasteroids. The isolation of withanolide T from the leaves ofPhysalis angulata L. is described and its spectral characteristics are given. Institute of the Chemistry of Plant Substances, Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 371–376, May–June, 1990.