- Synthesis and antituberculosis activity of several steroids from 3αacetoxy-5βpregn-16-En-20-one
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The semicarbazone and isonicotinoylhydrazone of 5βpregn-2-en-20-one, which was prepared from 3βacetoxy-5βpregn-16-en-20-one, were synthesized for the first time. The antituberculosis activity of these and semicarbazones and isonicotinoylhydrazones of saturated, unsaturated, and adamantane-modified ketosteroids synthesized by us earlier was studied in vitro experiments.
- Sikharulidze,Nadaraia,Kakhabrishvili
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Read Online
- UNUSUAL HIGH REACTIVITIES OF Δ5 STEROIDS IN PALLADIUM CATALYZED HYDROGENATION
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Hydrogenation of a mixture of 3β-hydroxyandrost-5-en-17-one or cholesterol with α-pinene has revealed that the Δ5 steroids are more reactive than α-pinene over palladium while α-pinene is much more reactive than the Δ5 steroids with other platinum metals.
- Nishimura, Shigeo,Takahashi, Izumi,Shiota, Michio,Ishige, Masayoshi
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Read Online
- ANDROSTENEDIONE METABOLISM IN EPITHELIAL CELLS DERIVED FROM EARLY-LACTATION HUMAN MILK
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Epithelial cells derived from duct epithelium were cultured from early lactation human milk in medium supplemented with 15percent fetal calf serum, insulin (0.3 u/ml), cortisol 21-sodium succinate (6 μg/ml) and amikacin (50 μg/ml).The capacity of these cells to metabolize androstenedione to estrone, estradiol and C19 metabolites was studied during continuous culture.After extraction of the medium, the products were subjected to phenolic partition and separated by thin-layer and paper chromatography, followed by recrystallization to constant specific activity.The study demonstrated a progressive increase in the formation of estrone and testosterone over the first 24 h in culture, while estradiol formation showed an initial 2-4 h lag, then increased slowly.The C19 compounds identified were androsterone, 5α-androstanedione, epiandrosterone, dihydrotestosterone and etiocholanolone. 5α-Androstanedione and androsterone were the major 5α-reduced metabolites.Since these cells are derived from normal duct epithelium, their metabolic characteristics may be more representative of normal breast tissue than those of tissue removed from patients with pathological breast disorders.
- Perel, E.,Stolee, K. J.,Kharlip, L.,Blackstein, M. E.,Killinger, D. W.
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Read Online
- Synthesis of guggulsterone derivatives as potential anti-austerity agents against PANC-1 human pancreatic cancer cells
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E- and Z-guggulsterones and nine guggulsterone derivatives (GSDs) were synthesized and evaluated for their preferential cytotoxicity against human PANC-1 cell in nutrient deprived medium utilizing antiausterity strategy. Among the synthesized compounds, GSD-1 and GSD-7 showed potent cytotoxicity against PANC-1 cells under nutrient-deprived conditions in a concentration dependent manner, with a PC50 value of 1.6 μM and 3.2 μM, respectively. The effect of GSD-1 and GSD-7 was further evaluated in a real time using live cell imaging. Both of these compounds altered PANC-1 cell morphology, leading to cell death at sub micromolar concentration range. GSD-1 and GSD-7 also inhibited PANC-1 cell colony formation in a concentration-dependent manner. GSD-1 and GSD-7 are lead structure for the anti-austerity drug development.
- Kohyama, Aki,Yokoyama, Rei,Dibwe, Dya Fita,El-Mekkawy, Sahar,Meselhy, Meselhy R.,Awale, Suresh,Matsuya, Yuji
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Read Online
- 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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- Catalytic removal of tert-butyldimethylsilyl (TBS) ether by PVP-I
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A mild, efficient and rapid protocol the deprotection of alcoholic TBDMS ethers using PVP-1 as catalyst in methanol, the procedure of deprotection of various TBDMS ethers were found to be very convenient, easy work-up, high yielding.
- Ke, Yanxiong,Lu, Guangying,Ren, Jiangmeng,Wang, Di,Zeng, Bu-Bing
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- Steroid compound 3-site hydroxyl configuration inversion method
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The invention discloses a steroid compound 3-site hydroxyl configuration inversion method. The method specifically comprises the following steps that (1) a steroid compound containing a 3-site hydroxyl reacts with an acyl chloride compound; (2) the product obtained in the step (1) and a substituting agent are subjected to SN2 nucleophilic substitution reaction under existing of a phase transfer catalyst; and (3) the product obtained in the step (2) is subjected to a hydrolysis reaction. Compared with a Mitsunobu method, the method does not need to use triphenylphosphine and azodiformate pricedhigher, and accordingly the production cost is greatly lowered; meanwhile, a p-nitrobenzoic acid derivative which seriously affects the water environment does not need to be used, and therefore the method is more environmentally friendly. The method adopts cesium acetate/18-crown ether-6 system to conduct 3-site hydroxyl configuration inversion, can remarkably reduce occurrence of side reactions,accordingly a higher reaction yield is obtained, and the method is finally applicable to industrialized production.
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Paragraph 0037; 0042; 0043
(2018/12/14)
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- Abiraterone acetate reducing impurity and preparation method thereof
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The invention discloses an abiraterone acetate reducing impurity and a preparation method thereof. The impurity is 17-(3-pyridyl) androstane-3 beta-acetoxyl. The preparation method of the impurity includes the steps: taking dehydroepiandrosterone as a starting material; performing catalytic hydrogenation by palladium carbon to obtain (3 beta)-3-hydroxy-17-sterone; performing reaction by hydrazine hydrate to obtain 17-hydrazono-androstane-3 beta-alcohol; performing iodine substitution to obtain 17-iodine-androstane-3 beta-alcohol; reacting the 17-iodine-androstane-3 beta-alcohol with borane reagents under palladium catalysis to obtain 17-(3-pyridyl) androstane-3 beta-alcohol; performing acetic anhydride acetylation to obtain the abiraterone acetate reducing impurity 17-(3-pyridyl) androstane-3 beta-acetoxyl.
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Paragraph 0017
(2017/10/22)
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- New technology for synthesizing epiandrosterone by using 3beta-hydroxypregna-16-ene-20-one-3-acetate
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The invention provides a new technology for synthesizing epiandrosterone by using 3beta-hydroxypregna-16-ene-20-one-3-acetate. The new technology comprises the following steps of using the 3beta-hydroxypregna-16-ene-20-one-3-acetate as raw materials; oximating, rearranging, alcoholizing and hydrolyzing, so as to obtain the epiandrosterone. The new technology has the characteristics that the total yield rate of the epiandrosterone is 78% or above; by adopting the technical scheme, the hydrogenation reaction is not needed, the reaction condition is mild, and the problem of overhigh industrial cost caused by using palladium chloride-calcium carbonate as a catalyst in the traditional method is solved; the amount of byproducts is small; the operation is simple, the pollution is little, the yield rate is high, and the like; the new technology is suitable for industrialized production.
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Paragraph 0017; 0041; 0042
(2017/08/30)
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- NEUROACTIVE STEROIDS, COMPOSITIONS, AND USES THEREOF
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Provided are methods of evaluating or treating a patient, e.g., a patient having a disorder described herein, comprising: a) optionally, acquiring a patient sample; b) acquiring an evaluation of and/or evaluating the sample for an alteration in the level S24(S)-hydroxycholesterol compared to a reference standard.
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Paragraph 0528; 0529; 0530
(2016/02/16)
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- Stereo selective one-step reduction in the steroid skeleton 4 - ene -3 - ketone as a 3 α - hydroxy - 5 β - hydrogen A/B cis structure method
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The invention relates to a method for one-step reduction of a 4-ene-3-one structure in a steroid skeleton into an A/B cis-3a-hydroxy-5b-hydrogen structure, belonging to the fields of organic chemistry and drug synthesis. According to the method, under the conditions of room temperature and an environment of absolute ethyl alcohol, cuprous chloride is used as a catalyst and sodium borohydride is used as a reducing agent for high-selectivity conversion of the 4-ene-3-one structure of 4-AD, ADD and derivatives thereof into the A/B cis-3a-hydroxy-5b-hydrogen structure. According to results of X-diffraction results, an androstane-3a-hydroxy-5b-hydrogen-17-one product prepared by using the method has a stereo structure; reaction conditions are mild and simple; used reagents are cheap and easily available; operation is convenient; good repeatability is realized, and high yield is obtained. The method provided by the invention lays a good foundation for exploitation of resourceful utilization of sterol and for research on synthesis of drugs like ursodesoxycholic acid, chenodeoxycholic acid, deoxycholic acid and ecdyson with the A/B cis-structure with non-cholic acid type steroids as raw materials.
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Paragraph 0022; 0041; 0042; 0043
(2017/02/17)
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- Characterization of hamster NAD+-dependent 3(17)β-hydroxysteroid dehydrogenase belonging to the aldo-keto reductase 1C subfamily
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The cDNAs for morphine 6-dehydrogenase (AKR1C34) and its homologous aldo-keto reductase (AKR1C35) were cloned from golden hamster liver, and their enzymatic properties and tissue distribution were compared. AKR1C34 and AKR1C35 similarly oxidized various xenobiotic alicyclic alcohols using NAD+, but differed in their substrate specificity for hydroxysteroids and inhibitor sensitivity. While AKR1C34 showed 3α/17β/20α-hydroxysteroid dehydrogenase activities, AKR1C35 efficiently oxidized various 3β- and 17β-hydroxysteroids, including biologically active 3β-hydroxy-5α/β-dihydro-C19/C21-steroids, dehydroepiandrosterone and 17β-estradiol. AKR1C35 also differed from AKR1C34 in its high sensitivity to flavonoids, which inhibited competitively with respect to 17β-estradiol (Ki 0.11-0.69 μM). The mRNA for AKR1C35 was expressed liver-specific in male hamsters and ubiquitously in female hamsters, whereas the expression of the mRNA for AKR1C34 displayed opposite sexual dimorphism. Because AKR1C35 is the first 3(17)β-hydroxysteroid dehydrogenase in the AKR superfamily, we also investigated the molecular determinants for the 3β-hydroxysteroid dehydrogenase activity by replacement of Val54 and Cys310 in AKR1C35 with the corresponding residues in AKR1C34, Ala and Phe, respectively. The mutation of Val54Ala, but not Cys310Phe, significantly impaired this activity, suggesting that Val54 plays a critical role in recognition of the steroidal substrate.
- Endo, Satoshi,Noda, Misato,Ikari, Akira,Tatematsu, Kenjiro,El-Kabbani, Ossama,Hara, Akira,Kitade, Yukio,Matsunaga, Toshiyuki
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p. 425 - 434
(2015/11/27)
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- NEUROACTIVE STEROIDS, COMPOSITIONS, AND USES THEREOF
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Described herein are neuroactive steroids of the Formula (I): (Formula (I)) or a pharmaceutically acceptable salt thereof; wherein R1a and R1b are as defined herein. Such compounds are envisioned, in certain embodiments, to behave as GABA modulators. The present invention also provides pharmaceutical compositions comprising a compound of the present invention and methods of use and treatment, e.g., such for inducing sedation and/or anesthesia.
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Page/Page column 72
(2015/02/02)
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- Rabbit 3-hydroxyhexobarbital dehydrogenase is a NADPH-preferring reductase with broad substrate specificity for ketosteroids, prostaglandin D2, and other endogenous and xenobiotic carbonyl compounds
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3-Hydroxyhexobarbital dehydrogenase (3HBD) catalyzes NAD(P) +-linked oxidation of 3-hydroxyhexobarbital into 3-oxohexobarbital. The enzyme has been thought to act as a dehydrogenase for xenobiotic alcohols and some hydroxysteroids, but its physiological function remains unknown. We have purified rabbit 3HBD, isolated its cDNA, and examined its specificity for coenzymes and substrates, reaction directionality and tissue distribution. 3HBD is a member (AKR1C29) of the aldo-keto reductase (AKR) superfamily, and exhibited high preference for NADP(H) over NAD(H) at a physiological pH of 7.4. In the NADPH-linked reduction, 3HBD showed broad substrate specificity for a variety of quinones, ketones and aldehydes, including 3-, 17- and 20-ketosteroids and prostaglandin D2, which were converted to 3α-, 17β- and 20α-hydroxysteroids and 9α,11β- prostaglandin F2, respectively. Especially, α-diketones (such as isatin and diacetyl) and lipid peroxidation-derived aldehydes (such as 4-oxo- and 4-hydroxy-2-nonenals) were excellent substrates showing low Km values (0.1-5.9 μM). In 3HBD-overexpressed cells, 3-oxohexobarbital and 5β-androstan-3α-ol-17-one were metabolized into 3-hydroxyhexobarbital and 5β-androstane-3α,17β-diol, respectively, but the reverse reactions did not proceed. The overexpression of the enzyme in the cells decreased the cytotoxicity of 4-oxo-2-nonenal. The mRNA for 3HBD was ubiquitously expressed in rabbit tissues. The results suggest that 3HBD is an NADPH-preferring reductase, and plays roles in the metabolisms of steroids, prostaglandin D2, carbohydrates and xenobiotics, as well as a defense system, protecting against reactive carbonyl compounds.
- Endo, Satoshi,Matsunaga, Toshiyuki,Matsumoto, Atsuko,Arai, Yuki,Ohno, Satoshi,El-Kabbani, Ossama,Tajima, Kazuo,Bunai, Yasuo,Yamano, Shigeru,Hara, Akira,Kitade, Yukio
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p. 1366 - 1375
(2013/11/19)
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- The regio- and stereo-selective reduction of steroidal 4-en-3-ones using Na2S2O4/NaHCO3 and CuCl/NaBH 4
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This paper describes the regio- and stereoselective reduction of a.
- Wang, Chunli,Chen, Xiaoyu,Huang, Yaoqing,Yang, Jesse,Chen, Ying
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p. 1339 - 1346
(2013/11/19)
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- NEUROACTIVE STEROIDS, COMPOSITIONS, AND USES THEREOF
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Compounds are provided according to Formula (I) and pharmaceutically acceptable salts thereof, wherein Z is a group of the formula (i), (ii), (iii), (iv), or (v), and wherein L1, L2, L3, X1, X2, Y, Rz4, Rz5, Rz6, n, R1, R2, R3a, R3b, R4a, R4b, R6a, R6b, R7a, R7b, R11a, R11b, R14, R17, R19, R20, R23a, R23b, and R24 are as defined herein, and pharmaceutical compositions thereof. Compounds of the present invention are contemplated useful for the prevention and treatment of a variety of CNS-related conditions in mammals.
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Paragraph 00356
(2013/03/26)
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- Characterization of rabbit aldose reductase-like protein with 3β-hydroxysteroid dehydrogenase activity
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In this study, we isolated the cDNA for a rabbit aldose reductase-like protein that shared an 86% sequence identity to human aldo-keto reductase (AKR)1 1B10 and has been assigned as AKR1B19 in the AKR superfamily. The purified recombinant AKR1B19 was similar to AKR1B10 and rabbit aldose reductase (AKR1B2) in the substrate specificity for various aldehydes and α-dicarbonyl compounds. In contrast to AKR1B10 and AKR1B2, AKR1B19 efficiently reduced 3-keto-5α/β-dihydro-C19/C21/C24-steroids into the corresponding 3β-hydroxysteroids, showing Km of 1.3-9.1 μM and kcat of 1.1-7.6 min-1. The stereospecific reduction was also observed in the metabolism of 5α- and 5β- dihydrotestosterones in AKR1B19-overexpressing cells. The mRNA for AKR1B19 was ubiquitously expressed in rabbit tissues, and the enzyme was co-purified with 3β-hydroxysteroid dehydrogenase activity from the lung. Thus, AKR1B19 may function as a 3-ketoreductase, as well as a defense system against cytotoxic carbonyl compounds in rabbit tissues. The molecular determinants for the unique 3-ketoreductase activity were investigated by replacement of Phe303 and Met304 in AKR1B19 with Gln and Ser, respectively, in AKR1B10. Single and double mutations (F303Q, M304S and F303Q/M304S) significantly impaired this activity, suggesting the two residues play critical roles in recognition of the steroidal substrate.
- Endo, Satoshi,Matsunaga, Toshiyuki,Kumada, Sho,Fujimoto, Airi,Hara, Akira,Ohno, Satoshi,El-Kabbani, Ossama,Hu, Dawei,Toyooka, Naoki,Mano, Jun'Ichi,Tajima, Kazuo
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p. 23 - 30,8
(2020/08/20)
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- Novel steroid inhibitors of glucose 6-phosphate dehydrogenase
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Novel derivatives of the steroid DHEA 1, a known uncompetitive inhibitor of G6PD, were designed, synthesized, and tested for their ability to inhibit this dehydrogenase enzyme. Several compounds with approximately 10-fold improved potency in an enzyme assay were identified, and this improved activity translated to efficacy in a cellular assay. The SAR for steroid inhibition of G6PD has been substantially developed; the 3β-alcohol can be replaced with 3β-H-bond donors such as sulfamide, sulfonamide, urea, and carbamate. Improved potency was achieved by replacing the androstane nucleus with a pregnane nucleus, provided a ketone at C-20 is present. For pregnan-20-ones incorporation of a 21-hydroxyl group is often beneficial. The novel compounds generally have good physicochemical properties and satisfactory in vitro DMPK parameters. These derivatives may be useful for examining the role of G6PD inhibition in cells and will assist the future design of more potent steroid inhibitors with potential therapeutic utility.
- Hamilton, Niall M.,Dawson, Martin,Fairweather, Emma E.,Hamilton, Nicola S.,Hitchin, James R.,James, Dominic I.,Jones, Stuart D.,Jordan, Allan M.,Lyons, Amanda J.,Small, Helen F.,Thomson, Graeme J.,Waddell, Ian D.,Ogilvie, Donald J.
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scheme or table
p. 4431 - 4445
(2012/09/11)
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- Biotransformation of testosterone and progesterone by Penicillium digitatum MRC 500787
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The biotransformation of testosterone and progesterone by Penicillium digitatum MRC 500787 for 5 days is described. The biotransformation of testosterone afforded 5α-androstane-3,17-dione, 3α-hydroxy-5α- androstan-17-one, 3β-liydroxy-5α-androstan-17-one and androst-4-ene-3,17-dione. The biotransformation of progesterone afforded 5α-pregnane- 3,20-dione.
- Yildirim, Kudret,Gulsan, Fatih,Kupcu, Ilknur
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experimental part
p. 675 - 683
(2011/08/03)
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- One-pot reductive cleavage of exo-olefin to methylene with a mild ozonolysis-Clemmensen reduction sequence
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A one-pot exo-olefin reductive cleavage was for the first time developed. The reaction could proceed under a mild condition avoiding the use of hazardous and expensive reagents. Meanwhile, a TMSCl-mediated Clemmensen reduction in alcoholic solvent was also examined.
- Xu, Shu,Toyama, Takayuki,Nakamura, Jun,Arimoto, Hirokazu
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scheme or table
p. 4534 - 4537
(2010/10/02)
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- MEDICINAL APPLICATIONS OF BENZOIC ACID HYDRAZONES SYNTHESIZED ON THE BASIS OF STEROIDAL TIGOGENIN
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Novel benzoic acid hydrazones of 5α-androstan-3, 17-dione have been prepared on the basis of steroidal tigogenin of the plant Yucca gloriosa. The hvdrazones of the General Formula (I), General Formula (II) and General Formula (III) as shown in the accompanying Figure of the drawing are synthesized. The hydrazones have shown promising anti-T.B., anti-cancer and anti-HIV activity revealing immense potential as more efficacious, less toxic drugs with fewer undesirable side effects. They could also prove valuable in correcting hormonal abnormalities that cause severe health problems.
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Page/Page column 7
(2009/12/27)
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- Method for distinguishing methicillin resistant S. aureus from methicillin sensitive S. aureus in a mixed culture
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The present invention provides isolated oligonucleotides and methods for detecting a methicillin resistant Staphylococcus aureus in a sample, including a sample that comprises nucleic acid molecules of higher biological complexity than that of amplified nucleic acid molecules.
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- Investigation on the regioselectivities of intramolecular oxidation of unactivated C-H bonds by dioxiranes generated in Situ
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We found that dioxiranes generated in situ from ketones 1-6 and Oxone underwent intramolecular oxidation of unactivated C-H bonds at δ sites of ketones to yield tetrahydropyrans. From the trans/cis ratio of oxidation products 1a and 2a as well as the retention of the configuration at the δ site of ketone 5, we proposed that the oxidation reaction proceeds through a concerted pathway under a spiro transition state. The intramolecular oxidation of ketone 6 showed the preference for a tertiary δ C-H bond over a secondary one. This intramolecular oxidation method can be extended to the oxidation of the tertiary γ′ C-H bond of ketones 9 and 10. For ketone 11 with two δ C-H bonds and one γ′ C-H bond linked respectively by a sp3 hydrocarbon tether and a sp2 ester tether, the oxidation took place exclusively at the δ C-H bonds. Finally, by introducing proper tethers, regioselective hydroxylation of steroid ketones 12-14 have been achieved at the C-17, C-16, C-3, and C-5 positions.
- Wong, Man-Kin,Chung, Nga-Wai,He, Lan,Wang, Xue-Chao,Yan, Zheng,Tang, Yeung-Chiu,Yang, Dan
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p. 6321 - 6328
(2007/10/03)
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- Copper(II) chloride dihydrate: A catalytic agent for the deprotection of tetrahydropyranyl ethers (THP ethers) and 1-ethoxyethyl ethers (EE ethers)
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Tetrahydropyranyl ethers (THP groups) and 1-ethoxyethyl ethers (EE groups) are removed upon refluxing in 95% EtOH or Me2CO-H2O (95:5) in the presence of a catalytic amount of copper(II) chloride dihydrate (2-5 mol%).
- Wang, Jianbo,Zhang, Chao,Qu, Zhaohui,Hou, Yihua,Chen, Bei,Wu, Peng
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p. 294 - 295
(2007/10/03)
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- The hydroxylation of some 13α-methylsteroids by Cephalosporium aphidicola
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The Fungus, Cephalosporium aphidicola, has been shown to hydroxylate 5α,13α-androstan-3,17-dione and the 3β-alcohol at the C-1α and C-7α positions, whereas the corresponding compounds in the normal 13β-methyl series are hydroxylated at the C-11α and C-14α positions. Both series were hydroxylated at the 5α position. There was some epimerization of the axial 3α-alcohols to the equatorial 3β-epimers.
- Boynton, Juliette,Hanson, James R.,Hunter, A. Christy
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p. 951 - 956
(2007/10/03)
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- Heterogeneous Catalysis in Carbonyl Regeneration from 1,3-Dithiolanes and 1,3-Dithianes by Zirconium Sulfophenyl Phosphonate
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Layered zirconium sulfophenyl phosphonate was found to be an efficient heterogeneous catalyst for mild hydrolysis of 1,2 dithiolanes and 1,3 dithianes to their corresponding carbonyl compounds.
- Curini, Massimo,Marcotullio, Maria Carla,Pisani, Emanuela,Rosati, Ornelio,Costantino, Umberto
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p. 769 - 770
(2007/10/03)
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- Formation of 5α steroids by biotranformation involving the 5 α-reductase activity of Penicillium decumbens
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The biotransformation of a series of Δ4-3-ketosteroids by the Penicillium decumbens ATCC 10436 has been investigated. Conversion to the 5α-dihydrosteroid was observed substrates of the androsterone and pregne series: the reaction is tolerant of non-polar substituents (Cl and CH3) at C-4 of the substrate, but does not occur in the presence of a 4-hydroxyl group, or with additional unsaturation at the Δ1 or Δ6 positions. A-nor, B-nor, 3-deoxy-, and 3,5-cycloandrostanes are not reduced, but 6-methylenestestosterone is converted to a 6-methylene-5α-dihydro derivative. Several biotransformations are reported which involve oxidoreductase activity at C-3 and/or C-17, either concomitant or independent of Δ4 reduction: the substrate specificity of the oxidoreductase processes has been examined and defined by the use of 3α-hydroxy, 3β-hydroxy, 3-keto, 17β-keto substituted steroids. In this way, the existence in P. decumbens of 3β-hydroxy-3-keto and 17β-hydroxy-17-keto oxidoreductases has been demonstrated.
- Holland, Herbert L.,Dore, Sophia,Xu, Weili,Brown, Frances M.
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p. 642 - 647
(2007/10/02)
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- Reduction of steroidal ketones and enones by sodium dithionite in presence of phase transfer catalyst
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Sodium dithionite has been effectively used in the reduction of steroidal ketones and enones with remarkable selectivity and high yields under phase transfer catalysis (PTC) conditions to give alcohols and ketones respectively. An application of these selectivities is demonstrated by reducing an important steroid intermediate 16-dehydropregnenolone acetate to pregnenolone acetate in very high yields.
- Akamanchi,Patel,Meenakshi
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p. 1655 - 1660
(2007/10/02)
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- Synthesis and characterization by1H and13C nuclear magnetic resonance spectroscopy of 17α-hexanoic derivatives of 5α-dihydrotestosterone and testosterone
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The synthesis and characterisation of 17α-(6′-hexanoic acid) derivatives of 5α-dihydrotestosterone and testosterone, useful as ligands for affinity chromatography purification or as precursors for affinitylabeling of androgen-binding proteins, is described. Alkynylation of 3-ethylenedioxy-, 3β-hydroxy-, and 3β,5-dihydroxy-5α-androstan-17-one precursors with the potassium derivative of 5-hexyn-1-ol led to the corresponding 17α-(6′-hydroxyhex-1′-ynyl) derivatives, which were hydrogenated over 10% Pt-C catalyst to give 17α-(6′-hydroxyhexyl) derivatives. Chromic acid oxidation of the primary hydroxy group of the 3-ethylenedioxy-17-hexyl intermediate into carboxylic acid followed by acid cleavage of the 3-ketal group gave 17α-(5′-carboxypentyl)-5α-dihydrotestosterone, which was also obtained directly by chromic acid oxidation of the 3β-hydroxy intermediate. Chromic acid oxidation of the primary hydroxy group of the 3β,5α-dihydroxy precursor resulted in a 5α-hydroxy-3-oxo intermediate, which was dehydrated to give 17α-(5′-carboxypentyl)testosterone. The 17α configuration of these derivatives and of synthetic precursors was established by comparing their molecular rotations and their 1H and 13C nuclear magnetic resonance (NMR) spectra including solvent effects, with data reported for 17α- or 17β-substituted steroid analogs as well as with 1H and 13C NMR reference data recorded in this work for 17α-ethynyltesfosterone, 17α-ethynyl-19-nortestosterone, 17α-ethyl-19-nortestosterone, 17αmethyltestosterone, and 17α-methyl-5α-dihydrotestosterone.
- Mappus, Elisabeth,Renaud, Melanie,De Ravel, Marc Rolland,Grenot, Catherine,Cuilleron, Claude Y.
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p. 122 - 134
(2007/10/02)
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- 16-substituted androstanes and 16-substituted androstenes
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Compounds of the formula: STR1 are useful as anti-cancer, anti-obesity, anti-diabetic, anti-coronary agents, anti-aging agents, anti-hypolipidemic agents and anti-autoimmune agents.
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- Homoandrostan-17-one and homoandrosten-17-ones
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Compounds of the formula: STR1 useful as anti-cancer agents, anti-obesity agents, anti-hyperglycemic agents, anti-aging agents, anti-hyperglycemic agents and anti-autoimmune agents.
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- A New Procedure for Dethioacetalization via Equilibrium Exchange with Aqueous Acetone, Paraformaldehyde and Amberlyst 15 as Acidic Catalyst
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Carbonyl compounds were regenerated from corresponding Ethanediyl S,S-Acetals via equilibrium exchange with aqueous acetone, paraformaldehyde and Amberlyst 15, as acidic catalyst, at 80 deg C.
- Ballini, Roberto,Petrini, Marino
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p. 336 - 337
(2007/10/02)
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- Cerium(IV)-Mediated Synthesis of Tetrahydrofuranyl Ethers
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The reaction of tetrahydrofuran with an alcohol in the presence of ceric triethylammonium nitrate provides a convenient and general procedure for protecting the hydroxyl function.Tetrahydrofuranyl ethers of primary, secondary and tertiary alcohols were obtained in good yields.
- Maione, Anna M.,Romeo, A.
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p. 250 - 251
(2007/10/02)
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- REGIOSELECTIVE REDUCTION OF POLYKETONES ON SILICA GEL SURFACE WITH BORANE-TRIMETHYLAMINE COMPLEX
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Steroidal diones and trione, bicyclic diones (7 and 8) and a tricyclic dione were adsorbed on silica gel and reduced with BH3*NMe3.The carbonyl groups at C-3 of the steroids, at C-4 of 7 and at C-3 of 8 were reduced regioselectively.The FT-IR spectra of 5α- and 5β-androstane-3,17-dione adsorbed on silica gel were measured.
- Gohzu, Shun-ichi,Tada, Masahiro
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- Steroids. Part 21. Photorearrangement of Steroidal Nitronate Salts and a N-Butyl Spiro-oxaziridine
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Irradiation, at 254 nm, of ethanol solutions of nitro-steroids in the presence of an excess of sodium ethoxide gave a range of products including hydroxamic acids, ketones, and alkenes possibly derived from the anions of the N-hydroxyoxaziridines.Alternatively, the ketones and hydroxamic acids may be derived from the anions of the hydroxy-nitroso compounds.The proportions of products depend on the ring size and stereochemistry and the photoreactions differ significantly from those observed for N-alkyl spiro-oxaziridines including a steroidal N-butyl spiro-oxaziridine.
- Edge, Graham J.,Imam, Syed H.,Marples, Brian A.
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p. 2319 - 2326
(2007/10/02)
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- Action de l'anhydride acetique et des chlorures de benzoyle et de p-toluene sulfonyle sur des nitrones derivees de ceto-17 steroides. Conditions conduisant a un rearrangement ou a une fonctionnalisation
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The reaction of the title reagents under anhydrous conditions and in the presence of base leads to steroidal derivatives functionalised at position 16; whereas, in the presence of water, paratoluenesulphonyl chloride gives 17-aza-D-homo lactams by ring expansion, and use of benzoyl chloride promotes a hydrolytic fragmentation.In contrast to earlier studies, the formation of an oxaziridine under aqueous alkaline conditions was not observed in this work.These results, when considered in conjunction with those previously obtained, enable the course of these reactions to be determined as a function of the reaction conditions.
- Cherest, M.,Lusinchi, X.
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p. 227 - 232
(2007/10/02)
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- STUDY OF THE DIRECT EFFECT OF LHRH AGONIST ON TESTICULAR 17-HYDROXYLASE AND 5α-REDUCTASE ACTIVITIES IN NON-HYPOPHYSECTOMIZED ADULT RATS TREATED WITH AN ANTI-LUTEINIZING HORMONE SERUM
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In order to study both direct and pituitary-mediated mechanisms of action of the LHRH analogue 6, des-Gly-NH210>LHRH ethylamide upon testicular steroidogenesis in adult rat, we compared the effects of the agonist when administered alone or concomitantly with an anti-LH serum to non-hypophysectomized rats.Testicular steroid contents and in vitro progesterone and testosterone metabolism were determined.Anti-LH serum administration was able to prevent 5α-reductase stimulation by the agonistic peptide, but not the inhibition of 17-hydroxylase activity.These data suggest that modulation of 17-hydroxylase involves both direct and pituitary-mediated processes, while 5α-reductase stimulation is mainly if not only due to a pituitary-mediated mechanism.
- Carmichael, Rejean,Belanger, Alain
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- SYNTHESIS OF 5α-ANDROSTANE-3α,16α,17β-TRIOL FROM 3β-HYDROXY-5-ANDROSTEN-17-ONE
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5α-Androstane-3α,16α,17β-triol was synthesized from 3β-hydroxy-5-androsten-17-one.The procedure involved catalytic hydrogenation of 3β-hydroxy-5-androsten-17-one to 3β-hydroxy-5α-androstan-17-one.This was followed by conversion of the 3β-hydroxy group to 3α-benzoyloxy group by the Mitsunobu reaction.Further treatment with isopropenyl acetate yielded 5α-androsten-16-ene-3α,17-diol 3-benzoate 17-acetate.This was then converted to 3α,17-dihydroxy-5α-androstan-16-one 3-benzoate 17-acetate via the unstable epoxide intermediate after treatment with m-chloroperoxybenzoic acid.LiAlH4 reduction of this compound formed 5α-androstane-3α,16α,17β-triol. 1H and 13C NMR of various steroids are presented to confirm the structure of this compound.
- Newaz, S. N.,Tcholakian, Robert K.
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p. 445 - 456
(2007/10/02)
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- CHEMOSELECTIVITY IN MOLYBDENUM CATALYZED ALCOHOL AND ALDEHYDE OXIDATIONS
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Hydrogen peroxide in the presence of (NH4)6Mo7O24*4H2O and potassium carbonate is a chemoselective method to oxidize secondary alcohols to ketones and to oxidize aldehydes to acids, the latter also accelerated by cerium chloride.
- Trost, Barry M.,Masuyama, Yoshiro
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p. 173 - 176
(2007/10/02)
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- PHOSPHINERHODIUM COMPLEXES AS HOMOGENEOUS CATALYSTS. XVI. STEREOSELECTIVE HYDROGENATION OF CYCLIC KETONES
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Cyclic ketones have been hydrogenated stereoselectively with various phosphinerhodium complexes as catalysts.Systems containing phosphines of high basicity and consequently forming RhIII dihydrides as active species yielded mainly the thermodynamically more stable alcohol isomers.Catalysts prepared from aryl-type phosphines of low basicity and modified with Et3N, which contain RhI monohydrides as active complexes, afforded the less stable alcohol isomers as the major products.The ratio of RhIII and RhI hydrides, which determines the stereoselectivity of the catalysts prepared in situ could be changed by suitable choice of base.
- Toros, Szilard,Kollar, Laszlo,Heil, Balint,Marko, Laszlo
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p. 377 - 384
(2007/10/02)
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- Microbiological Transformations. XVI. Transformation of 5α- and 5β-Dihydro, and 1- and 6-Dehydro Derivatives of Testosterone and Androstenedione by Means of Rhodotorula mucilaginosa Strain
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The following transformation of 5α- and 5β-dihydro derivatives of testosterone and androstenedione by means of Rhodotorula mucilaginosa has been observed: reduction of the carbonyl group on C-3 to both possible alcohols in the 5α-series and only to one alcohol (3α) in the 5β-series.In the transformation of 1- and 6-dehydro derivatives of testosterone and androstenedione, reduction in ring A was completely inhibited.The carbonyl or hydroxy groups at C-17 in both series of substrates underwent interconversion.
- Draczynska, Bozena,Tlomak, Elzbieta,Dmochowska-Gladysz, Jadwiga,Siewinski, Antoni
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- OXIDATION OF ALCOHOLS BY ELECTROCHEMICALLY REGENERATED NICKEL OXIDE HYDROXIDE. SELECTIVE OXIDATION OF HYDROXYSTEROIDS
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Primary alcohols, α,ω-diols and secondary alcohols are easily transformed into carboxylic acids, dicarboxylic acids or ketones, respectively, by heterogeneous oxidation with nickel oxide hydroxide electrochemically regenerated at a nickel hydroxyde electrode.The results are discussed in comparison to those of the nickel peroxide and chromic acid oxidation.The oxidation rate decreases with increasing steric hindrance of the alcohol, thus allowing the selective oxidation of the 3-position in hydroxysteroids.
- Kaulen, Johannes,Schaefer, Hans-J.
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p. 3299 - 3308
(2007/10/02)
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- Stereoselective and Regioselective Reduction of Steroid Ketones by Potassium Tri(R,S)-s-butyl)borohydride
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Potassium tri(R,S-s-butyl)borohydride reduces 3-oxo-steroids of the 5α- and 5β-series to the axial alcohol under conditions in which the 17- and 20-ketone groups remain unaffected.
- Goendoes, Gyoergy,Orr, James C.
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p. 1239 - 1240
(2007/10/02)
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- Glucosiduronidation and esterification of androsterone by human breast tumors in vitro
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The metabolism of 3H-androsterone was studied in homogenates (fortified with uridine 5'-diphosphoglucuronic acid and andenosine 3'- phosphate 5'-phosphosulfate) of eighteen breast tumors, one muscle underlying the primary breast carcinoma and metastatic axillary lymph nodes from a patient with suspected primary breast cancer. The major metabolites identified were less polar than androsterone. On saponification these lipoidal derivatives afforded androsterone as the only product (3 to 48%). Unmetabolized androsterone and lesser quantities of epiandrosterone, 5α-andorstane-3α, 17β-diol and 5α-androstane-3,17-dione comprised the free steroid fraction. Androsterone glucosiduronate was isolated (0.17-4.1%) from eight breast tumor homogenates and fromthe node tissue incubation (17%). There was no apparent correlation between glucuronyltransferase activity and histolpathology or estrogen receptor content.
- Raju,Kadner,Levitz,Kaganowicz,Blaustein
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p. 399 - 407
(2007/10/02)
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