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-1,3,24-triol. Alliospirosides C and D are cepagenin 1-O-[O--L-rhamnopyranosyl-(12)-L-arabinopyranoside] and 1-O-[O--L-rhamnopyranosyl-(12)-O--D-galactopyranoside], respectively.Institute of the Chemistry of Plant Substances, Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 843–849, November–December, 1987.     

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.     

Steroids of the spirostan and furostan series from plants of the genus Allium. Structure of anzurogenin A from Allium suvorovii and A. stipitatum

The collective fruit of the cocultivatedAllium suvorovii Rgl. andA. stipitatum Rgl. (familyLiliaceae) has yielded a new genin of the spirostan series — anzurogenin A, which is 2,3,5-trihydroxy-(25R)-spirostan-6-one.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 68–73, January–February, 1988.     

Steroids of the spirostan and furostan series from plants of the genus Allium. XXV. Structure of anzurogenin B from Allium suvorovii and Allium Stipitatum

A new genin of the spirostan series — anzurogenin B having the structure of 2,5-epoxy-(25R)-spirostan-3,6-diol — has been isolated form the collective fruit of the cocultivatedAllium suvorovii Rgl. andAllium stipitatum Rgl. (family Liliaceae).Institute of the Chemistry of Plant Substances, Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 218–221, March–April, 1988.     

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.     

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)-2,3,5,24-tetrahydroxy-5-spirostan-6-one. Anzuroside is the 24-O--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.     

Steroids of the spirostand and furostan series from plants of the genusAllium. II. The structure of alliospiroside B fromAllium cepa

A new steroid glycoside — alliospiroside B (I) — has been isolated from the collective fruit ofAllium cepa L. On the basis of chemical transformations and with the aid of physicochemical measurements it has been established that compound (I) has the structure of (25S)spirost-5-ene-1β,3β-diol 1-O-[O-α-L-rhamnopyranosyl-(1 → 2)-β-D-galactopyranoside. Compound (I) C₃₉H₆₂O₃, mp 200–202°C (from ethanol). [α] _D ²⁰ ?110.9±2° (c 1.01; pyridine) was obtained by extracting the collective fruit ofA. cepa with ethanol folowed by the column chromatographic separation of the combined glycosides on silica gel. The acid hydrolysis of (I) gave (25S)-ruscogenin (II), C₂₇H₄₂O₄, mp 189–191°C, [α] _D ²³ ?104.1±2° (c 0.98; pyridine). The¹H and¹³C NMR spectra are given for both compounds and the IR spectrum for compound (I).     

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--D-glucofuranosyloxy-(25S)-furost-5,20(22)-diene-1, 3-diol 1-sulfate, and nolinofuroside H is the sodium salt of 1--D-fucopyranosyloxy-26--D-glucopyranosyloxy-(25S)-furost-5,20(22)-dinen-1-3-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.     

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.     

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).     

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-1,3-diol 1-O--D-fucopyranoside (nolinospiroside C, II), (25S)-furost-5-ene-1,3,22,26-tetraol 1-O--D-fucopyranoside (nolinofuroside A, III), and (25S)-furost-5-ene-1, 3, 22, 26-tetraol 1-O--D-fucopyranoside 26-O--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.     

Steroids of the spirostan and furostan series from Nolina microcarpa IV. Structures of nolinogenin,nolinospiroside B,and nolinofuroside B

A glycoside has been isolated from the plantNolina microcarpa S. Wats. (family Dracaenaceae) which has been called nolinofuroside B and has the structure of 6-methoxy-3,5-cyclo-(25S)-furostan-1,22,26-triol 1-O--D-fucopyranoside 26-O--D-glucopyranoside (I). Enzymatic hydrolysis of the bioside (I) yielded nolinospiroside B (III) and nolinogenin (IV). The latter is 6-methoxy-3,5-cyclo-(25S)-spirostan-6-ol, and glycoside (III) is its 1-O--D-fucopyranoside.M. V. Frunze Simferopol' State University. Institute of Chemistry of Plant Substances, Uzbekistan Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 218–224, March–April, 1992.     

Secondary-ion mass spectrometry of lycotetraosides of the spirostan and furostan series

The secondary-ion mass spectra of seven steroid lycotetraosides have been obtained by the SIMS method. On the use of a glycerol matrix, all the compounds of the spirostan series, including those with an additional carbohydrate substituent a C-24, formed the (M+H)⁺ ions, while a lycotetraoside of the furostan series formed the (M–H₂O+H)⁺ ion. They subsequently decomposed by the alternative successive elimination of the terminal carbohydrate units of the lycotetraose. Substituents at C-25 and C-26 were ejected in the form of glucose molecules. Fragments of the aglycon and of the lycotetraoside moieties of the molecules were recorded. When NaCl was added to the same matrix, all the compounds gave preferentially the (M+Na)⁺ and (M+2Na–H)⁺ ions.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. All-Union Scientific-Research Institute of Agricultural Biotechnology, Lenin All-Union Academy of Agricultural Sciences, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 53–58, January–February, 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.     

Steroids of the furostan and spirostan series from Nolina microcarpa II. structures of nolinospiroside D and nolinofurosides D, E, and F

Proofs are given of the structures of two new glycosides of the furostan series isolated from the leaves of the plantNolina microscarpa S. Wats. (family Dracaenaceae). Nolinofuroside D is (25S)-furost-5-ene-1,3,22,26-tetraol 1-O--D-galactopyranoside 26-O--D-glucopyranoside (I), and nolinofuroside F is (25S)-furost-5-ene-1,3,22,26-tetraol 1-O--D-fucopyranoside 26-O--D-glucopyranoside 3-O--L-rhamnopyranoside (VII). The latter was characterized as its 22-O-methyl ether (VIII). Nolinofuroside E (IV) has the structure of (25S)-furost-5-ene-1,3,22,26-tetraol 26-O--glucopyranoside 1-O-[O--L-rhamnopyranosyl-(12)--D-fucopyranoside], which followed from the structure of the fermentation product (VI). The products of the fermentation of the above-named compounds were present in the plant in only trace amounts. Only one of them — nolinospiroside D (III) — has not been described previously. This monoside of the spirostan series is (25S)-spirost-5-ene-1,3-diol 1-O--D-galactopyranoside.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. 678–686, September–October, 1991.     

Inhibition of highly purified porcine kidney Na,K-ATPase by steroid glycosides of the spirostan and furostan series and a study of structure-activity relationships

A comparative investigation has been made of the action of 14 steroid glycosides of the spirostan and furostan series on highly purified Na,K-ATPase from the medullary layer of porcine kidneys (∼90% purity in terms of protein). It has been shown that alliospirosides A, B, and D, isolated from the collective fruit ofAllium sepa L., are capable of inhibiting the activity of the Na,K-ATPase The inhibition of the activity of the transport enzyme by alliospirosides A and B is of the uncompetitive type and by alliospiroside D of the competitive type. It is desirable to test alliospirosides on the intact organism. Institute of Physiology, Academy of Sciences of the Republic of Uzbekistan. Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 558–566, July–August, 1993.     

Inhibition of highly purified porcine kidney Na,K-ATPase by steroid glycosides of the spirostan and furostan series and a study of structure-activity relationships

A comparative investigation has been made of the action of 14 steroid glycosides of the spirostan and furostan series on highly purified Na,K-ATPase from the medullary layer of porcine kidneys (90% purity in terms of protein). It has been shown that alliospirosides A, B, and D, isolated from the collective fruit ofAllium sepa L., are capable of inhibiting the activity of the Na,K-ATPase The inhibition of the activity of the transport enzyme by alliospirosides A and B is of the uncompetitive type and by alliospiroside D of the competitive type. It is desirable to test alliospirosides on the intact organism.Institute of Physiology, Academy of Sciences of the Republic of Uzbekistan. Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 558–566, July–August, 1993.