1239-31-2Relevant academic research and scientific papers
Elemental fluorine. Part 22. Fluorination of 3β-acetoxy-5α-androstan-17-one using fluorine and Selectfluor
Chambers, Richard D.,Nakano, Takashi,Parsons, Mandy,Sandford, Graham,Batsanov, Andrei S.,Howard, Judith A.K.
, p. 811 - 816 (2008)
Reactions of 3β-acetoxy-5α-androstan-17-one with elemental fluorine and Selectfluor are reported and give contrasting results. Fluorine gives a mixture of mono-fluorinated steroids in which fluorine atoms are attached to tertiary carbon sites whereas Selectfluor gives fluoro-steroid systems arising from electrophilic aliphatic substitution of the most sterically accessible secondary saturated positions. The identities of the fluoro-steroid products were determined by NMR analysis and X-ray crystallography.
Diastereoselective synthesis of C60/steroid conjugates
Ruiz, Alberto,Coro, Julieta,Almagro, Luis,Ruiz, Jose A.,Molero, Dolores,Maroto, Enrique E.,Filippone, Salvatore,Herranz, Maria Angeles,Martinez-Alvarez, Roberto,Sancho-Garcia, Juan Carlos,Di Meo, Florent,Suarez, Margarita,Martin, Nazario
, p. 2819 - 2826 (2013)
The design and synthesis of fullerene-steroid hybrids by using Prato's protocol has afforded new fullerene derivatives endowed with epiandrosterone, an important naturally occurring steroid hormone. Since the formation of the pyrrolidine ring resulting from the 1,3-dipolar cyloaddition reaction takes place with generation of a new stereogenic center on the C2 of the five-membered ring, the reaction proceeds with formation of a diastereomeric mixture [compounds 6 and 7 in 70:30 ratio, 8 and 9 in 26:74 ratio (HPLC)] in which the formation of the major diasteroisomers 6 and 9 is consistent with an electrophilic attack of [60]fullerene on the Re face of the azomethine ylide directed by the steroidic unit. The chiroptical properties of these conjugates reveal typical Cotton effects in CD spectra that have been used to assign the absolute configuration of the new fulleropyrrolidines. The electrochemical study of the new compounds reveals the presence of four quasi-reversible reduction waves which are cathodically shifted in comparison with the parent C 60, thus ascertaining the proposed structures.
A new simple and high-yield synthesis of 5α-dihydrotestosterone (DHT), a potent androgen receptor agonist
Purushottamachar, Puranik,Njar, Vincent C.O.
, p. 1530 - 1534 (2012)
We have devised an efficient procedure for the synthesis of 5α-dihydrotestosterone (DHT) (1) starting from 3β-hydroxy-5α- androstan-17-one, providing the product in unprecedented 82% yield. A reported method of using toxic Jones reagent is replaced by milder oxidizing agent (NMO/TPAP) in the synthesis of a key intermediate 17β-[(tert- butyldimethylsilyl)oxy]-5α-androstan-3-one (18). This new procedure is simple, does not require special apparatus/precautions or chromatographic purification in most of the steps.
Synthesis and biological evaluation of D-ring fused 1,2,3-thiadiazole dehydroepiandrosterone derivatives as antitumor agents
Cui, Hai-Wei,Peng, Shihong,Gu, Xiang-Zhong,Chen, Huang,He, Yuan,Gao, Wei,Lv, Fang,Wang, Jin-Hua,Wang, Yan,Xie, Jia,Liu, Ming-Yao,Yi, Zhengfang,Qiu, Wen-Wei
, p. 126 - 137 (2016)
A series of D-ring fused 1,2,3-thiadiazole DHEA derivatives were synthesized and investigated for their activity against the growth of various tumor cell lines using the sulforhodamine B (SRB) assay. It is amazing that for these compounds, T47D cell line was much more sensitive than other tumor cell lines. The most potent saturated N-heterocyclic derivatives showed similar antitumor effect with the positive control compound ADM (adriamycin) on T47D cells, that was 44–60 folds more potent than the lead compound DHEA. Most compounds with potent antitumor activity displayed low toxicity on normal human fibroblasts (HAF). Especially compound 25 (CH33) showed an IC50 of 0.058 μM on T47D cells and its selectivity index (SI) between HAF and T47D was 364, which was 214 folds better than ADM (SI = 1.7). The apoptosis, colony formation and transwell migration assays of 25 were performed on T47D cell line. The primary mechanism study showed that 25 caused a dose-dependent induction of apoptosis, and induced phosphorylation of EphA2 and EphB3 in T47D cells. The in vivo antitumor effect of 25 was also observed in T47D tumor-bearing mice without obvious toxicity.
Synthesis of a human long-term oxymetholone metabolite
Kratena, Nicolas,Biedermann, Nina,Stojanovic, Biljana,G?schl, Lorenz,Weil, Matthias,Enev, Valentin S.,Gmeiner, Günter,G?rtner, Peter
, (2019)
A long-term metabolite of the doping agent oxymetholone (OXM-M2, 17β-hydroxymethyl-2,17α-methyl-18-norandrost-13-en-3-one) which has been identified by GC-MS/MS was synthesized from commercially available materials. Two efficient synthetic routes to access both C-17 epimers of tentative metabolites were developed. The identity and molecular configuration of the in vivo metabolite: 17β-hydroxymethyl-2α,17α-methyl-18-norandrost-13-en-3-one was confirmed by single crystal X-ray diffraction.
Steroid–Fullerene Hybrids from Epiandrosterone: Synthesis, Characterization and Theoretical Study
Almagro, Luis,Hernández-Castillo, David,Ortiz, Orlando,Alonso, Dayana,Ruiz, Alberto,Coro, Julieta,Herranz, María ángeles,Molero, Dolores,Martínez-álvarez, Roberto,Suárez, Margarita,Martín, Nazario
, p. 4512 - 4522 (2018)
New hybrid fullerene–steroid derivatives were prepared by using the Bingel–Hirsch protocol, by treatment of [60]fullerene with malonates bearing the appropriate steroid moieties obtained, in turn, from the functionalization of epiandrosterone, an important naturally occurring steroid hormone. Monocycloadduct C60-steroid conjugates were obtained by functionalization of ring A or ring D of the steroid moiety. We have also described the multistep preparation of a [60]fullerene hybrid dumbbell endowed with two fullerene units connected through an epiandrosterone molecule by a cyclopropanation reaction. The new compounds have been spectroscopically characterized and their redox potentials, determined by cyclic voltammetry, reveal three reversible reduction waves for monocycloadducts (8, 9 and 11, 12), whereas dumbbell-type derivative 10 exhibits the best electron-accepting abilities of the Bingel-type fullerene–steroid series. Theoretical calculations at semiempirical (AM1) and single point B3LYP-D3/6-31G+(d,p) levels have predicted the most stable conformations for the hybrid compounds and allow explaining the observed regioselectivity in the cyclopropanation reaction with dimalonate 7 during the synthesis of the dumbbell derivative.
Visible-Light-Driven Dehydrogenative Coupling of Primary Alcohols with Phenols Forming Aryl Carboxylates
Ishida, Naoki,Kawasaki, Tairin,Murakami, Masahiro,Tosaki, Tomohiro
supporting information, p. 7683 - 7687 (2021/10/12)
A preparative method for obtaining aryl esters from aliphatic primary alcohols and phenols was developed. The reaction proceeds under the irradiation of visible light at ambient temperature, dispensing with any oxidant or hydrogen acceptor. Primary alcohols having a variety of functional groups are successfully esterified with phenols. The produced esters can be utilized as the precursor of various carbonyl compounds.
Development of Selective Steroid Inhibitors for the Glucose-6-phosphate Dehydrogenase from Trypanosoma cruzi
Fredo Naciuk, Fabrício,Do Nascimento Faria, Jéssica,Gonc?lves Eufrásio, Amanda,Torres Cordeiro, Artur,Bruder, Marjorie
supporting information, p. 1250 - 1256 (2020/07/27)
Chagas disease is a parasitic infection affecting millions of people across Latin America, imposing a dramatic socioeconomic burden. Despite the availability of drugs, nifurtimox and benznidazole, lack of efficacy and incidence of side-effects prompt the identification of novel, efficient, and affordable drug candidates. To address this issue, one strategy could be probing the susceptibility of Trypanosoma parasites toward NADP-dependent enzyme inhibitors. Recently, steroids of the androstane group have been described as highly potent but nonselective inhibitors of parasitic glucose-6-phosphate dehydrogenase (G6PDH). In order to promote selectivity, we have synthesized and evaluated 26 steroid derivatives of epiandrosterone in enzymatic assays, whereby 17 compounds were shown to display moderate to high selectivity for T. cruzi over the human G6PDH. In addition, three compounds were effective in killing intracellular T. cruzi forms infecting rat cardiomyocytes. Altogether, this study provides new SAR data around G6PDH and further supports this target for treating Chagas disease.
Steroid compound 3-site hydroxyl configuration inversion method
-
, (2018/12/14)
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.
Pd-mediated cross-coupling of C-17 lithiated androst-16-en-3-ol-access to functionalized arylated steroid derivatives
Koch, Vanessa,Br?se, Stefan
supporting information, p. 92 - 95 (2016/12/27)
Herein, we report on Pd-mediated cross-coupling of vinyllithium steroids and aryl bromides to introduce various substituted aryls at C-17 of steroidal frameworks based on the structure of epi-androsterone. Compared to other C-C cross-couplings, this method turned out to be an easy and competitive access to biologically interesting C-17 modified steroids.
