- Steroidal saponins from the underground parts of Hosta longipes and their inhibitory activity on tumor promoter-induced phospholipid metabolism
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Phytochemical study on the underground parts of Hosta longipes gave six new steroidal saponins together with a known one. The structures of the new compounds were determined by detailed analysis of their 1H- and 13C-NMR spectra including two-dimensional NMR spectroscopy, acid-catalyzed hydrolysis followed by chemical correlation, and by comparison with spectral data of known compounds. The isolated saponins and their aglycones were examined for inhibitory activity on 12-O-tetradecanoylphorbol-13-acetate (TPA)-stimulated 32P-incorporation into phospholipids of HeLa cells to identify new antitumor-promoter compounds.
- Mimaki,Kanmoto,Kuroda,Sashida,Nishino,Satomi,Nishino
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- The cephalostatins. 23. Conversion of hecogenin to a steroidal 1,6-dioxaspiro[5.5]nonane analogue for cephalostatin 11
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Cephalostatin 1 (1) has proved to be a remarkably potent cancer cell growth inhibitor. Since this steroidal alkaloid constituent of the marine worm Cephalodiscus gilchristi possesses a complex structure, providing preclinical supplies by total synthesis continues to be challenging. Therefore, syntheses of less complex structural modifications of this important pyrazine have also received substantial attention. Herein are summarized the synthesis of [5.5]spiroketal 5, a simplified right-side steroidal unit of 1, in seven steps from hecogenin acetate (11) with an overall yield of 4.6%. Consistent with other SAR studies, such reduction in structural complexity compared to 1 led to loss of cancer cell growth inhibitory activity against the P388 lymphocytic leukemia cell line.
- Pettit, George R.,Moser, Bryan R.,Herald, Delbert L.,Knight, John C.,Chapuis, Jean-Charles,Zheng, Xing
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- SPIROSTANOL GLYCOSIDES FROM AGAVE CANTALA
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Two spirostanol glycosides, cantalasaponins -2 and -4 were isolated from the methanolic extract of the rhizomes of Agave cantala and were characterized.The first glycoside was found to be lethal against Biomphalaria glabrata, tha snail vector of the disease schistosomiasis, at a concentration of 7 ppm. Key Word Index - Agave cantala; Agavaceae; saponins; spirostanol glycosides; schistosomiasis; Biomphalaria glabrata.
- Pant, G.,Sati, O. P.,Miyahara, K.,Kawasaki, T.
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- A TRIGLUCOSIDE OF HECOGENIN FROM FRUITS OF AGAVE CANTALA
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The fruits of Agave cantala contain a steroidal saponin which is a glycoside of hecogenin with three molecules of glucose.Its structure has been established as α-D-glucopyranosyl(1->4)α-D-glucopyranosyl(1->4)α-D-glucopyranosyl(1->3)hecogenin.Key Word Index - Agave cantala; Agavaceae; saponin; hecogenin triglucoside.
- Varshney, I. P.,Jain, D. C.,Srivastava, H. C.
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- Photoinduced Deoxygenative Borylations of Aliphatic Alcohols
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A photochemical method for converting aliphatic alcohols into boronic esters is described. Preactivation of the alcohol as a 2-iodophenyl-thionocarbonate enables a novel Barton–McCombie-type radical deoxygenation that proceeds efficiently with visible light irradiation and without the requirement for a photocatalyst, a radical initiator, or tin or silicon hydrides. The resultant alkyl radical is intercepted by bis(catecholato)diboron, furnishing boronic esters from a diverse range of structurally complex alcohols.
- Wu, Jingjing,B?r, Robin M.,Guo, Lin,Noble, Adam,Aggarwal, Varinder K.
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p. 18830 - 18834
(2019/11/22)
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- Deoxygenative Borylation of Secondary and Tertiary Alcohols
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Two different approaches for the deoxygenative radical borylation of secondary and tertiary alcohols are presented. These transformations either proceed through a metal-free silyl-radical-mediated pathway or utilize visible-light photoredox catalysis. Readily available xanthates or methyl oxalates are used as radical precursors. The reactions show broad substrate scope and high functional-group tolerance, and are conducted under mild and practical conditions.
- Friese, Florian W.,Studer, Armido
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supporting information
p. 9561 - 9564
(2019/06/21)
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- Steroidal glycosides from the bulbs of Bessera elegans and their cytotoxic activities
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Examination of the bulbs of Bessera elegans (Liliaceae) led to isolation of nine new and five known steroidal glycosides. The structures of the nine compounds were determined based on the results of spectroscopic analysis, including two-dimensional NMR, and hydrolysis followed by chromatographic and spectroscopic analysis. The isolated compounds and derivatives were evaluated for cytotoxicity against HL-60 human promyelocytic leukemia cells, A549 human lung adenocarcinoma cells, and TIG-3 normal human diploid fibroblasts. One compound, the pseudo-furostanol glycoside, induced apoptosis in HL-60 and A549 cells in a time-dependent manner and cell-cycle arrest at the G0/G1 phase in A549 cells.
- Matsuo, Yukiko,Akagi, Nana,Hashimoto, Chisato,Tachikawa, Fumito,Mimaki, Yoshihiro
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p. 244 - 256
(2014/01/06)
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- Synthetic pathway to 22,23-dioxocholestanic chain derivatives and their usefulness for obtaining brassinosteroid analogues
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Recognizing the functionality of the pentacyclic steroidal derivative 7a as important synthon to obtain new brassinosteroid analogs, we have accomplished the derivatization of hecogenin, a sapogenin from the 25R serie containing a carbonyl group at C-12, to a 22,23-dioxocholestanic chain derivative. Starting from hecogenin acetate (5a) or hecogenin tosylate (5b), we obtained two pentacyclic derivatives (7a and 7b) which were subjected to an oxidation reaction on the double bond at C-12(23) to obtain a 22,23- dioxocholestanic chain, with the regeneration of the carbonyl group at C-12. Reduction of the carbonyl groups lead to the 20-epi-12,23-dihydroxy-22-oxo system 11a-b. The absolute configuration of compound 11a was established by X-ray diffraction analysis.
- Gómez-Calvario, Víctor,Arenas-González, Ailed,Meza-Reyes, Socorro,Montiel-Smith, Sara,Vega-Báez, José Luis,Sandoval-Ramírez, Jesús,Hernández-Linares, María Guadalupe
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p. 902 - 908
(2014/02/14)
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- Synthesis of the antiproliferative agent hippuristanol and its analogues via Suárez cyclizations and Hg(II)-catalyzed spiroketalizations
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A full account of the synthesis of hippuristanol and its analogues is described. Hecogenin acetate was identified as a suitable and economical starting material for this work, and substrate-controlled stereoselection was obtained throughout the construction of the key spiroketal unit. Suárez cyclization was first used, but Hg(II)-catalyzed spiroketalization of the 3-alkyne-1,7-diol motif was finally identified as the most convenient strategy.(Figure Presented)
- Ravindar, Kontham,Reddy, Maddi Sridhar,Lindqvist, Lisa,Pelletier, Jerry,Deslongchamps, Pierre
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experimental part
p. 1269 - 1284
(2011/04/26)
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- Efficient synthetic approach to potent antiproliferative agent hippuristanol via Hg(II)-catalyzed spiroketalization
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Figure Presented. The steroidal natural product hippuristanol targets eukaryotic translation initiation factor (eIF)4A which plays a pivotal role in translation in eukaryotic cells. Now an efficient synthesis of hippuristanol from 11-ketotigogenin is reported. The synthesis features a rapid construction of a spiroketal unit via Hg(OTf)2-catalyzed oxidation/ spiroketalization of the 3-alkyn-1,7-diol motif.
- Ravindar, Kontham,Reddy, Maddi Sridhar,Lindqvist, Lisa,Pelletier, Jerry,Deslongchamps, Pierre
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supporting information; experimental part
p. 4420 - 4423
(2010/12/18)
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- Synthesis of a new cytotoxic cephalostatin/ritterazine analogue from hecogenin and 22-epi-hippuristanol
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A new cephalostatin/ritterazine analogue was prepared from the commercially available hecogenin acetate and the natural cytotoxic steroid 22-epi-hippuristanol. The method involved the reductive dimerization of enaminoketones (condensation of α-aminoketones) and condensation between an enaminoketone and an α-hydroxyketone. The new analogue showed higher cytotoxic activity than the cytotoxic 22-epi-hippuristanol against MDA-MB-231, A-549 and HT-29 cultured tumor cell lines.
- Poza, Javier Jesus,Rodriguez, Jaime,Jimenez, Carlos
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scheme or table
p. 58 - 63
(2010/04/26)
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- Steroidal saponins from the whole plants of Agave utahensis and their cytotoxic activity
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Phytochemical investigation of the whole plants of Agave utahensis Engelm. (Agavaceae) has resulted in the isolation of 15 steroidal saponins (1-15), including five spirostanol saponins (1-5) and three furostanol saponins (11-13). Structures of compounds
- Yokosuka, Akihito,Mimaki, Yoshihiro
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experimental part
p. 807 - 815
(2010/05/18)
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- Filiasparosides A-D, cytotoxic steroidal saponins from the roots of Asparagus filicinus
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Four new steroidal saponins, filiasparosides A-D (1-4), together with known aspafiliosides A (5) and B (6) were isolated from the roots of Asparagus filicinus. The structures of these new compounds were elucidated by detailed spectroscopic study and chemical analysis. Compounds 1-6 were cytotoxic against human lung carcinoma (A549) and breast adenocarcinoma (MCF-7) tumor cell lines with EC50 values of 2.3-16.8 μg/mL. Compound 3 showed the most potent cytotoxicity, with EC50 values of 2.3 and 3.0 μg/mL toward A549 and MCF-7 cell lines, respectively.
- Zhou, Li-Bo,Chen, Tzu-Hsuan,Bastow, Kenneth F.,Shibano, Makio,Lee, Kuo-Hsiung,Chen, Dao-Feng
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p. 1263 - 1267
(2008/04/01)
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- The NMR studies on two new furostanol saponins from Agave sisalana leaves
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The detailed NMR studies and full assignments of the 1H and 13C spectral data for two new furostanol saponins isolated from Agave sisalana leaves are described. Their structures were established using a combination of 1D and 2D NMR techniques including 1H, 13C, 1H-1H COSY, TOCSY, HSQC, HMBC and HSQC-TOCSY, and also FAB-MS spectrometry and chemical methods. The structures were established as (25S)-26-(β-D-glucopyranosyl)-22ξ-hydroxyfurost-12-one-3β-yl-O- α-L-rhamnopyranosyl-(1→4)-β-D-glucopyranosyl-(1→3) -O-[O-β-D-glucopyranosyl-(1→2)]-O-β-D-glucopyranosyl-(1→4) -β-D-galactopyranoside (1) and (25S)-26-(β-D-glucopyranosyl)-22ξ- hydroxyfurost-5-en-12-one-3ξ-yl-O-α-L-rhamnopyranosyl-(1→4) -β-D-glucopyranosyl-(1→3)-O-[O-β-D-glucopyranosyl-(1→2)] -O-β-D-glucopyranosyl-(1→4)-β-D-galactopyranoside (2). Copyright
- Zou, Peng,Fu, Jing,Yu, He-Shui,Zhang, Jie,Kang, Li-Ping,Ma, Bai-Ping,Yan, Xian-Zhong
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p. 1090 - 1095
(2008/02/04)
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- Steroidal glycosides from the aerial parts of Polianthes tuberosa
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A chemical investigation of the aerial parts of Polianthes tuberosa resulted in the isolation of a new bisdesmosidic cholestane glycoside (1) and three new spirostanol saponins (2-4), along with a known cholestane glycoside. The structures of new glycosides were determined bY spectroscopic analysis, including 2D NMR spectroscopic data, and the results of hydrolytic cleavage. The isolated compounds were evaluated for their cytotoxic activity on HL-60 human promyelocytic leukemia cells.
- Mimaki, Yoshihiro,Yokosuka, Akihito,Sashida, Yutaka
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p. 1519 - 1523
(2007/10/03)
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- A new bioactive steroidal saponin, furcreastatin, from the plant Furcraea foetida
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Microbial and plant secondary metabolites were screened for compounds that are selectively cytotoxic to mutant p53-expressing mouse fibroblasts. As a result, furcreastatin, a novel steroidal saponin, was isolated from an EtOH extract of the leaves of Furcraea foetida. Furcreastatin consisted of hecogenin as the aglycone and a hexasaccharide containing D-galactose, L- rhamnose and four D-glucose residues. The structure was determined to be (3β,5α,25R)-3-hydroxyspirostan-12-one 3-O-[α-L-Rhap-(1→4)-β-D-Glcp- (1→3)-{β-D-Glcp-(1→3)-β-D-Glcp-(1→2)}-β-D-Glcp-(1→4)-β-D-Galp] by extensive NMR spectroscopic studies. Furcreastatin decreased the viability of mutant p53-overexpressing cells with an ED50 of 4.0 μg/mL, and decreased that of the parental cell-line with an ED50 of 9.6 μg/mL. (C) 2000 Elsevier Science Ltd.
- Itabashi, Masaki,Segawa, Kaoru,Ikeda, Yoko,Kondo, Shinichi,Naganawa, Hiroshi,Koyano, Takashi,Umezawa, Kazuo
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- TRANSFORMATIONS OF SOLASODINE AND DERIVATIVES OF HECOGENIN BY CUNNINGHAMELLA ELEGANS
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Incubation of (25R)-5α-spirostane-3β,12β-diol (rickogenin) with the fungus Cunninghamella elegans led to the formation of (25R)-7β,12β-dihydroxy-5α-spirostan-3-one, (25R)-5α-spirostan-3β,7β,12β-triol and (25R)-5α-spirostan-3β,7α,12α-triol.Incubation of (25R)-5α-spirostan-3,12-dione (hecogenone) with the same fungus gave rise to (25R)-5α-spirostan-3,7,12-trione.When the (22R,25R)-spirosolane, solasod-5-en-3β-ol (solasodine) was incubated with C. elegans, solasod-5-ene-3β,7β-diol, solasod-5-ene-3β,7α-diol and 3β-hydroxysolasod-5-en-7-one were produced.In contrast, incubation of solasodine with Penicillium patulum gave solasod-4-en-3-one and the 6-methylsalicylic acid salt of solasodine.
- Patel, Asmita V.,Blunden, Gerald,Crabb, Trevor A.
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p. 125 - 134
(2007/10/02)
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- 12-KETO STEROIDAL GLYCOSIDES FROM THE CAUDEX OF YUCCA GLORIOSA
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Eight new steroidal glycosides, tentatively named YS-VI, -VII, -VIII, -IX, -X, -XI, -XII, -XIII were isolated from the caudex of Yucca gloriosa along with P-1, YG-2 and YG-3 previously obtained from flowers.The structures of five of these compounds were elucidated as mexogenin 3-O-β-D-glucopyranosyl-(1->2)-β-D-galactopyranoside (YS-VI), gloriogenin 3-O-β-D-glucopyranosyl-(1->2)-3)>-β-D-glucopyranoside (YS-VII) and 3-O-β-D-glucopyransyl-(1->2)-3)>-β-D-galactopyranoside (YS-VIII), manogenin 3-O-β-lycotetraooside (YS-IX) and 3-O-α-L-rhamnopyranosyl-β-lycotetraoside (YS-X), respectively on the basis of chemical and spectral evidence.
- Nakano, Kimiko,Midzuta, Yukari,Hara, Yumiko,Murakami, Kotaro,Takaishi, Yoshihisa,Tomimatsu, Toshiaki
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p. 633 - 636
(2007/10/02)
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- STEROIDAL SAPONINS FROM CHLOROPHYTUM MALAYENSE
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Four new steroidal saponins, chloromalosides A-D, were isolated from the rhizomes of Chlorophytum malayense.On the basis of detailed chemical and spectroscopic evidence, the structures of chloromalosides A-D were elucidated to be neohecogenin 3-O-β-D-glucopyranosyl(1->2)-3)>-β-D-glucopyranosyl(1->4)-β-D-galactopyranoside, 26-β-D-glucopyranosyl-22-hydroxy-25(S)-5α-furostane-3β,26-diol-3-O-β-D-glucopyranosyl(1->2)-3)>-β-D-glucopyranosyl(1->4)-β-D-galactopyranoside, neohecogenin 3-O-β-D-xylopyranosyl(1->3)-2)>-β-D-glucopyranosyl(1->4)-2)>-β-D-galactopyranoside and neotigogenin 3-O-β-D-xylopyranosyl(1->3)-2)>-β-D-glucopyranosyl(1->4)-2)>-β-D-galactopyranoside, respectively.
- Xing-Cong, Li,Wang, De-Zu,Yang, Chong-Ren
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p. 3893 - 3898
(2007/10/02)
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- STEROIDAL SAPONINS FROM DIURANTHERA MAJOR
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In addition to chloromaloside A, three new steroidal saponins, diuranthosides A-C, were isolated from the fresh roots of Diuranthera major.On the basis of chemical and spectroscopic analysis, the structures of diuranthosides A-C were established as neotigogenin 3-O-β-D-glucopyranosyl(1->2)-3)>-β-D-glucopyranosyl(1->4)-β-D-galactopyranoside, neohecogenin 3-O-β-D-glucopyranosyl(1->3)-β-D-xylopyranosyl(1->3)-2)>-β-D-glucopyranosyl(1->4)-β-D-galactopyranoside and neohecogenin 3-O-β-D-glucopyranosyl(1->3)-β-D-glucopyranosyl(1->2)-3)-β-D-xylopyranosyl(1->3)>-β-D-glucopyranosyl(1->4)-β-D-galactopyranoside, respectively.
- Li, Xing-Cong,Wang, Yi-Fei,Wang, De-Zu,Yang, Chong-Ren
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p. 3899 - 3901
(2007/10/02)
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- Steroidal glycosides of Tribulus terrestris Linn.
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Besides β-sitosterol-β-D-glucoside and dioscin, two new steroidal glycosides, neohecogenin glucoside and tribulosin, isolated from the aerial part of Tribulus terrestris Linn. were respectively shown to be neohecogenin-3-O-β-D-glucopyranoside (2) and neotigogenin-3-O-β-D-xylopyranosyl(1->2)-3)>-β-D-glucopyranosyl(1->4)-2)>-β-D-galactopyranoside (7).
- Mahato, Shashi B.,Sahu, Niranjan P.,Ganguly, Amar N.,Miyahara, Kazumoto,Kawasaki, Toshio
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p. 2405 - 2410
(2007/10/02)
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- Separation of hecogenin-tigogenin mixtures
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A process for separating hecogenin-tigogenin mixtures which involves acetylating the mixed genins, then solvent recrystallization separation of the mixed genin acetates, crystallizing out hecogenin acetate from a non-polar solvent, tigogenin acetate from a polar solvent. A sequential sequence is contemplated to first recover the predominant genin, then the less-predominant genin. Preferred source materials are crude 5-25% sapogenin content acid hydrolyzates of Agave leaf juice. Specifically preferred is the acid hydrolyzate from fresh Agave leaf juice obtained prior to decortication.
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