57-91-0Relevant articles and documents
One-Step Chemo-, Regio- and Stereoselective Reduction of Ketosteroids to Hydroxysteroids over Zr-Containing MOF-808 Metal-Organic Frameworks
Llabrés i Xamena, F. X.,Mautschke, H.-H.
, p. 10766 - 10775 (2021/06/15)
Zr-containing MOF-808 is a very promising heterogeneous catalyst for the selective reduction of ketosteroids to the corresponding hydroxysteroids through a Meerwein-Ponndorf-Verley (MPV) reaction. Interestingly, the process leads to the diastereoselective synthesis of elusive 17α-hydroxy derivatives in one step, whereas most chemical and biological transformations produce the 17β-OH compounds, or they require several additional steps to convert 17β-OH into 17α-OH by inverting the configuration of the 17 center. Moreover, MOF-808 is found to be stable and reusable; it is also chemoselective (only keto groups are reduced, even in the presence of other reducible groups such as C=C bonds) and regioselective (in 3,17-diketosteroids only the keto group in position 17 is reduced, while the 3-keto group remains almost intact). The kinetic rate constant and thermodynamic parameters of estrone reduction to estradiol have been obtained by a detailed temperature-dependent kinetic analysis. The results evidence a major contribution of the entropic term, thus suggesting that the diastereoselectivity of the process is controlled by the confinement of the reaction inside the MOF cavities, where the Zr4+ active sites are located.
Preparation method of [3-14C] marked 17alpha-estradiol
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, (2019/06/07)
The invention belongs to the technical field of synthesis of compounds marked by radioisotope 14C, and provides a preparation method of [3-14C] marked 17alpha-estradiol. The preparation method includes the following steps that 17beta-acylated elollactone and 14C marked acetylchloride serve as starting materials, and a condensation reaction, a primary hydrolysis reaction, a Mitsunobu reaction, an aromatization reaction and a secondary hydrolysis reaction are carried out to obtain [3-14C] marked 17alpha-estradiol. The method has the advantages that the synthesis cost is low, the line is short and the product yield is high. Besides, the preparation method is easy to operate and suitable for large-scale production.
Catalytic properties of pristine and defect-engineered Zr-MOF-808 metal organic frameworks
Mautschke,Drache,Senkovska,Kaskel,Llabrés Xamena
, p. 3610 - 3616 (2018/07/29)
Various defect-engineered Zr-trimesate MOF-808 compounds (DE-MOF-808) have been prepared by mixing the tricarboxylate ligands with dicarboxylate ligands; viz. isophthalate, pyridine-3,5-dicarboxylate, 5-hydroxy-isophthalate, or 5-amino-isophthalate. The resulting mixed-ligand compounds, MOF-808-X (X = IP, Pydc, OH or NH2) were all found to be highly crystalline and isostructural to the unmodified MOF-808. Pristine MOF-808 showed better catalytic performance than a UiO-66 reference compound for the Meerwein-Ponndorf-Verley (MPV) reduction of carbonyl compounds. This was attributed to a higher availability of coordinatively unsaturated Zr4+ sites (cus) in MOF-808 upon removal of formate ions. Meanwhile, cus in UiO-66 are only located at defect sites and are thus much less abundant. Further improvement of the catalytic activity of defect-engineered MOF-808-IP and MOF-808-Pydc was observed, which may be related with the occurrence of less crowded Zr4+ sites in DE-MOF-808. The wider pore structure of MOF-808 with respect to UiO-66 compounds translates into a sharp improvement of the activity for the MPV reduction of bulky substrates, as shown for estrone reduction to estradiol. Interestingly, MOF-808 produces a notable diastereoselectivity towards the elusive 17-α-hydroxy estradiol.
Thermodynamic Meerwein-Ponndorf-Verley reduction in the diastereoselective synthesis of 17α-estradiol
Ahmed, Gulzar,Nickisch, Klaus
, p. 1 - 4 (2016/07/06)
The synthesis of 17α-hydroxy steroids generally requires multiple synthetic manipulations. The synthesis of 17α-estradiol is no exception, as this process involves the protection and release of the 3-hydroxy functional group. The diastereoselective reduction of the 17-keto-steroid can be utilized to prepare 17α-hydroxy-steroids. Here, 17α-estradiol was synthesized from commercially available estrone under thermodynamic Meerwein-Ponndorf-Verley (MPV) conditions in a single step, followed by simple chromatographic separation over silica gel. The remaining mixture of unreacted estrone and estradiols was easily recycled through Oppenauer oxidation to estrone, with an overall yield of 68% 17α-estradiol.
Application of in Situ FTIR for the Preparation of 17-α-Estradiol via Mitsunobu Reaction
Cardoso, Flávio S. P.,Mickle, Gregory E.,Da Silva, Marco A.,Baraldi, Patricia T.,Ferreira, Fabio B.
, p. 306 - 311 (2016/03/04)
An efficient synthesis of 17-α-estradiol 1 is described. Utilization of in situ IR allowed for an online monitoring of the key Mitsunobu reaction and development of a safe and reliable synthesis of 17-α-estradiol 1 in 78% overall yield over three steps. Benzoylation of 17-β-estradiol 2 is conducted at high regioselectivity under phase-transfer catalysis (PTC) conditions, followed by a Mitsunobu reaction to invert the chiral center at C-17 and provide intermediate 5, containing the core structure of 17-α-estradiol 1. Finally, the desired active pharmaceutical ingredient (API) is prepared by saponification of the remaining esters.
DNA-templated release of functional molecules with an azide-reduction- triggered immolative linker
Gorska, Katarzyna,Manicardi, Alex,Barluenga, Sofia,Winssinger, Nicolas
supporting information; scheme or table, p. 4364 - 4366 (2011/06/19)
Nucleic acid templated reactions have attracted significant attention for nucleic acid sensing. Herein we report a general design which extends the potential of nucleic acid templated reactions to unleash the function of a broad diversity of small molecules such as a transcription factor agonist, a cytotoxic or a fluorophore.
Pharmaceutical composition with tumor necrosis factor A and 2-methoxyestrone-3-0-sulphamate for inhibition of estrone sulphatase
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, (2008/06/13)
A composition is described. The composition comprises i) a compound comprising a sulphamate group (“a sulphamate compound”); and ii) a biological response modifier.
Halogenated sulphamate-, phosphonate-, thiophosphonate-, sulphonate- and sulphonamide- compounds as inhibitors of steroid sulphatase
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, (2008/06/13)
A compound is described. The compound has the formula (Ia) as presented in the FIG. 1; wherein: X is a ring having at least 4 atoms in the ring; K is hydrocarbyl group; Rh1 is an optional halo group; Rh2 is an optional halo group; at least one of Rh1 and Rh2 is present; Rs is any one of a sulphamate group, a phosphonate group, a thiophosphonate group, a sulphonate group or a sulphonamide group. The compound is capable of inhibiting steroid sulphatase (STS) activity.
17-Aryl linker derivatised estrogen 3-sulphamates as inhibitors of steroid sulphatase
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, (2008/06/13)
There is provided a compound comprising a steroidal ring system and a group R1 selected from any one of a sulphamate group, a phosphonate group, a thiophosphonate group, a sulphonate group or a sulphonamide group; wherein the D ring of the steroidal ring system is substituted by a group R2 of the formula —L—R3, wherein L is an optional linker group and R3 is an aromatic hydrocarbyl group.
