- Electrocatalytic oxidation production process and device for 19-normethyl-4-androstene-3, 17-diketone
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The invention discloses an electrocatalytic oxidation production process and device for 19-normethyl-4-androstene-3, 17-diketone, and the process comprises the following steps: adding 19-hydroxymethyl-4-androstene-3, 17-diketone, nitroxide free radicals and a mixed solvent into an anode chamber to form an anode reaction solution, adding an alkaline buffer solution into a cathode chamber, dividing the electrolytic reaction tank into a left pole chamber and a right pole chamber by a cation exchange membrane so that the anode reaction liquid is driven to circularly flow between the anode chamber and the left pole chamber of the electrolytic reaction tank, and the alkaline buffer solution is driven to circularly flow between the cathode chamber and the right pole chamber of the electrolytic reaction tank, carrying out electrocatalytic oxidation reaction to generate an aldehyde intermediate 19-formaldehyde-4-androstene-3, 17-diketone, and then directly heating and stirring to react to obtain the product 19-normethyl-4-androstene-3, 17-diketone. Compared with the existing process for preparing 19-normethyl-4-androstene-3, 17-diketone which has the technical problems of high cost, serious environmental pollution, low yield and the like, the process has the advantages of low production cost, high target product yield, short production period and the like.
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Paragraph 0028-0038
(2021/05/15)
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- Method for preparing 19-desmethyl-4-androstene-3,17-diketone by using one-pot method
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The invention discloses a method for preparing 19-desmethyl-4-androstene-3,17-diketone by using a one-pot method. The method for preparing 19-desmethyl-4-androstene-3,17-diketone comprises the step oftaking a compound 1 as a starting raw material, carrying out hydrogenation and condensation reaction by using the one-pot method, thus obtaining a 19-desmethyl-4-androstene-3,17-diketone coarse product 3, wherein reaction formulas are as follows: as shown in the specification. According to the method, the high-purity 19-desmethyl-4-androstene-3,17-diketone coarse product can be obtained under a total mole yield of 92 percent or above, so that the method is low in cost, environmentally friendly and suitable for industrial production.
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Paragraph 0019
(2018/04/03)
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- Preparation method of 19-demethylation-4-androstenedione
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The invention discloses a preparation method of 19-demethylation-4-androstenedione and belongs to the technical field of medical intermediate processing. The preparation method comprises the following steps: (1) carrying out esterification reaction; (2) carrying out ketalation; (3) carrying out reduction reaction; (4) carrying out hydrolysis reaction; (5) carrying out esterification reaction; (6) carrying out addition reaction; (7) carrying out cyclization and hydrolysis reaction; (8) carrying out oxidation, dechloridation and ring-opening reaction; and (9) carrying out oxidation and decarboxylation reaction. The preparation method disclosed by the invention has the advantages that environmental pollution is small, usage amounts of a solvent and water are smaller, temperature sensitivity is low, control is easy, and yield is high; a chlorinating agent is adopted, so that reaction yield is increased; 1,3-dichloro-5,5-dimethylhydantoin is adopted, so that the reaction yield is further increased; and sodium hydrogen carbonate is adopted, so that final decarboxylic reaction yield is increased, and external standards and appearance of a product can be improved.
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- Method for preparing 19-nor-4-androstene-3,17-dione
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The invention discloses a method for preparing 19-nor-4-androstene-3,17-dione. The method comprises the following steps: taking a compound 1 as an initial raw material, carrying out a hydrolysis reaction, a hydrogenation reaction and condensation reaction so as to obtain 19-nor-4-androstene-3,17-dione, wherein the reaction formula is as shown in the specification. According to the method disclosed by the invention, a high-purity 19-nor-4-androstene-3,17-dione product is obtained at the total molar yield of 83% or higher, and the method is low in cost, green, environmental-friendly and suitable for industrial production.
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- Preparation method of estra-4-ene-3,17-dione
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The invention provides a preparation method of estra-4-ene-3,17-dione. The method comprises the following steps: hydrogenation reaction: adding a first solvent and a palladium catalyst into a reaction container under the protection of nitrogen, stirring for 10 to 60 minutes, introducing hydrogen into the reaction container to replace the nitrogen, adding a raw material shown as a general formula I into the reaction container and stirring at the end of nitrogen replacement, heating to 10 to 60 DEG C, introducing hydrogen to react for 2 to 10 hours, separating the palladium catalyst out by using the nitrogen at the end of the reaction to obtain an intermediate solution of a compound shown as a general formula II, and keeping the intermediate solution for later use under the protection of the nitrogen; ring-closure reaction: concentrating the obtained intermediate solution to a viscous state under a normal pressure under the protection of the nitrogen, adding an acid-removing reagent into the viscous intermediate solution and stirring, reacting at the temperature of 60 to 100 DEG C for 0.5 to 5 hours, adding a second solvent into a solution obtained after the reaction, stirring for 10 to 30 minutes, dropwise adding reagent water, and cooling, filtering and drying to obtain the steroidal estrogen-4-ene-3,17-diketone shown as a general formula III, wherein a reaction route is shown in the description.
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Paragraph 0042; 0043; 0047; 0048; 0052; 0053; 0057; 0058
(2017/08/29)
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- Synthesis process of paricalcitol
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The invention discloses a synthesis process of paricalcitol. The synthesis process of the paricalcitol comprises the steps of adopting nandrolone as a raw material, oxidizing, carrying out wittig reaction, carrying out hydroxy protection, brominating, rearranging, carrying out dehydrobromination, carrying out addition, oxidizing, reducing, carrying out hydroxy deprotection, and opening ring to obtain the paricalcitol. The paricalcitol is used for preventing and treating secondary hyperthyroidism.
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Paragraph 0035; 0036
(2017/09/29)
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- New process for synthesizing steroid 3-one-4-ene
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The invention discloses a new process for synthesizing steroid 3-one-4-ene. The method comprises the steps: with steroid 3-hydroxy-5-ene as a starting material, in a nonprotic organic solvent, with air or oxygen as an oxidant and with a transition metal nitrate and a 2,2,6,6-tetramethylpiperidine-1-oxyl free radical or an analogue thereof as catalysts, oxidizing to obtain the steroid 3-one-4-ene. The method has the advantages of high yield, mild reaction conditions, easily controlled operation, low energy consumption, low cost, and safety; and the whole process is friendly to the environment, and is suitable for industrialization.
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Paragraph 0065; 0068; 0070
(2016/10/09)
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- 19-nor-4-androstene -3,17-dione method for the preparation of
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The invention provides a method for preparing 19- nor-4-androstene-3, 17-diketone. The preparation method comprises the following step: with a compound I as a raw material, carrying out a Grignard reaction, an oxidation and ring-closure reaction and a reduction and ring-closure reaction, and the reaction route is shown as follows. The starting raw material of the preparation method is relatively cheap, the product yield is high and the production cost can be saved. The formula is described in the description.
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Paragraph 0037; 0045
(2016/11/28)
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- Imitation of phase i oxidative metabolism of anabolic steroids by titanium dioxide photocatalysis
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The aim of this study was to investigate the feasibility of titanium dioxide (TiO2) photocatalysis for oxidation of anabolic steroids and for imitation of their phase I metabolism. The photocatalytic reaction products of five anabolic steroids were compared to their phase I in vitro metabolites produced by human liver microsomes (HLM). The same main reaction types - hydroxylation, dehydrogenation and combination of these two - were observed both in TiO2 photocatalysis and in microsomal incubations. Several isomers of each product type were formed in both systems. Based on the same mass, retention time and similarity of the product ion spectra, many of the products observed in HLM reactions were also formed in TiO2 photocatalytic reactions. However, products characteristic to only either one of the systems were also formed. In conclusion, TiO2 photocatalysis is a rapid, simple and inexpensive method for imitation of phase I metabolism of anabolic steroids and production of metabolite standards.
- Ruokolainen, Miina,Valkonen, Minna,Sikanen, Tiina,Kotiaho, Tapio,Kostiainen, Risto
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- Pd nanoparticles as catalysts for green and sustainable oxidation of functionalized alcohols in aqueous media
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The previously described catalyst system for the aerobic oxidation of alcohols, comprising palladium(II) acetate in combination with neocuproine in a 1:1 mixture of water and a water-miscible cosolvent such as ethylene carbonate or dimethylsulfoxide, was shown to involve palladium nanoparticles as the active catalyst. The latter are formed in situ or can be preformed by reduction of the palladium-neocuproine complex with hydrogen and they are stabilized by both the neocuproine ligand and the cosolvent. This catalyst system was successfully used for the selective aerobic oxidation of the steroidal secondary alcohols, nandrolone and 5α-pregnan-3α-ol-20-one, to the corresponding ketones.
- Mifsud, Maria,Parkhomenko, Ksenia V.,Arends, Isabel W.C.E.,Sheldon, Roger A.
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experimental part
p. 1040 - 1044
(2010/04/02)
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- Doping in sport-2. Quantification of the impurity 19-norandrostenedione in pharmaceutical preparations of norethisterone
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The finding of measurable amounts of 19-norandrostenedione in norethisterone tablets prompted us to develop an assay to quantify this steroid. 19-Norandrostenedione is an anabolic steroid whose use in sport is prohibited by the World Anti-Doping Agency (WADA). The assay was developed using isotope dilution and liquid chromatography-tandem mass spectrometry (LC-MS/MS) for the quantification of 19-norandrostenedione in norethisterone formulations, with [3,4-13C2]-19-norandrostenedione as the internal standard. The results showed amounts up to 1.01 ± 0.01 μg (mean ± S.E.M.) per tablet in those containing 5 mg of norethisterone or norethisterone acetate (0.02%, w/w) and up to 0.5 ± 0.01 μg (mean ± S.E.M.) per tablet (0.05%, w/w) in oral contraceptive tablets containing 0.35-1.5 mg of norethisterone or norethisterone acetate. No tablet tested exceeded the British Pharmacopoeia limit of 0.1% for this impurity.
- Walker, Christopher J.,Cowan, David A.,James, Vivian H.T.,Lau, Joanne C.Y.,Kicman, Andrew T.
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scheme or table
p. 335 - 340
(2009/06/08)
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- Microbial transformation of nandrolone decanoate by acremonium strictum
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Estr-4-en-3,17-dione II, 17β-hydroxyestr-4-en-3-one III, 15α-hydroxyestr-4-en-3,17-dione IV, and 15α,17β-dihydroxyestr- 4-en-3-one V were produced by microbial transformation of nandrolone decanoate I in the culture of Acremonium strictum PTCC 5282. Bioconversion characteristics observed were ester hydrolysis, oxidation, and hydroxylation. Each microbial product was purified chromatographically and characterized on the basis of spectral data obtained from 1H-NMR, 13C-NMR, FT-IR, MS, and physical constants such as melting point and optical rotation.
- Yazdi, Mojtaba Tabatabaei,Zanjanian, Seyedeh Maryam,Faramarzi, Mohammad Ali,Amini, Mohsen,Amani, Amir,Abdi, Khosrou
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p. 473 - 476
(2007/10/03)
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- The oxidation of 3-hydroxy-3-methyl-Δ4-steroids by chromium trioxide
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Oxidation of the allylic tertiary alcohols of 3-hydroxy-3-methyl-Δ 4-steroids by chromium trioxide in sulfuric acid leads to C-C bond fission together with the formation of a 3-methylestra-1,3,5(10)-triene from a 19-nor steroid and a 3β,4β-epoxy-5β-hydroxy compound from an androstane; the structure of the hydroxy-epoxide was established by X-ray crystallography.
- Uyanik, Cavit,Hanson, James R.,Hitchcock, Peter B.
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p. 795 - 797
(2007/10/03)
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- The hydroxylation of testosterone and some relatives by Cephalosporium aphidicola
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The fungus Cephalosporium aphidicola has been shown to hydroxylate testosterone, 19-nortestosterone, 1-dehydrotestosterone, 1α-methyltestosterone, androst-4-en-3-one, androst-4-en-3,17-dione and 17α-methyltestosterone predominantly at the C-6β position with a minor hydroxylation occurring at the C-14α position. 19-Nortestosterone was also hydroxylated at the C-10β position. In contrast to the hydroxylation of progesterone by this organism, hydroxylation at C-11α was a minor pathway.
- Hanson, James R.,Nasir, Habib,Parvez, Aslam
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p. 411 - 415
(2007/10/03)
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- Transition-metal catalyzed oxidations. 7. Zirconium-catalyzed oxidation of primary and secondary alcohols with hydroperoxides
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A new procedure for the oxidation (dehydrogenation) of primary and secondary alcohols employing Zr(O-t-Bu)4 or Zr(O-n-Pr)4/tert-butyl hydroperoxide/3 A molecular sieves is presented. Secondary alcohols - if not severely sterically hindered - are usually converted quantitatively to the corresponding ketones. Esters or acids can be by products in the reaction of primary alcohols. However, the aldehydes are obtained in good yield by lowering the reaction temperature, decreasing the amount of TBHP or replacing TBHP by cumene hydroperoxide (CHP), and/or exchanging the catalyst Zr(O-t-Bu)4 by Zr(O-n-Pr)4 or silica gel-supported Zr(OR)(x). A remarkable selectivity of equatorial alcohol groups (e.g., 11 and 13) is observed in contrast to chromium(VI)-based oxidations. Strongly chelating substrates such as furfuryl alcohol (18) or 1,2-diol 25 that prevent hydride transfer in the six-membered transition state A are not converted.
- Krohn, Karsten,Vinke, Ingeborg,Adam, Horst
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p. 1467 - 1472
(2007/10/03)
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- Zirconium alkoxide catalyzed Oppenauer oxidation using chloral as the hydride acceptor
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A new variation of the Oppenauer oxidation is presented with chloral as the hydride acceptor and Zr(O-t-Bu)4 or, for highly reactive carbonyl products, the heterogeneous system SiO2/Zr(O-n-Pr)(x), as the catalyst. The reaction proceeds under mild conditions (20°C) with a substoichiometric amount of Zr(O-t-Bu)4 (usually 20%). Primary and secondary allyl alcohols are converted in high yields to the corresponding carbonyl compounds.
- Krohn, Karsten,Knauer, Birgit,Kuepke, Jochen,Seebach, Dieter,Beck, Albert K.,Hayakawa, Michyay
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p. 1341 - 1344
(2007/10/03)
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- Novel Insertion, Rearrangement and Addition Products from Dihalogenocarbene Reactions with 5(10)-Unsaturated Steroids
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Novel insertion, rearrangement and addition products from dibromocarbene and dichlorocarbene reactions with 5(10)-unsaturated steroids have been identified.The dihalogenocarbenes were prepared under phase-transfer conditions (CHBr3- or CHCl3-NaOH), and from CHBr3-KOBut-Et2O, phenyl(trichloromethyl)mercury and sodium trichloroacetate.Evidence that the major products arise from an initial dihalogenocarbene reaction on the α face of the molecule is reported.The major products obtained from addition of CBr2 to 3,17-disubstituted estr-5(10)-enes, after ketal hydrolysis, were 19(S)-bromo-9α,19-cyclo-10α-androst-4-en-3-one and 3',3',19(S)-tribromo-3'H-9α,19-cyclopropa-5β,10α-androstan-3-one derivatives together with the 19,19-dibromo-5α,19-cyclo-10α-steroid adduct.No products from addition of CBr2 to the β-face of the double bond, as previously reported, were identified.Reactions of CCl2 gave, besides rearrangement products analogous to those obtained from CBr2, a 5α-hydroxy-9α,19α-cycloandrostane derivative, the 9α-CHCl2 insertion derivative and both α- and β-face addition products to the double bond.Structures were established by homonuclear and heteronuclear correlation and nuclear Overhauser effect NMR measurements and X-ray crystallography.
- Templeton, John F.,Ling, Yangzhi,Lin, Weiyang,Pitura, Randy J.,Marat, Kirk,Bridson, John N.
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p. 1149 - 1158
(2007/10/02)
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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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- Photoinduced Molecular Transformations. Part 112.Transformation of Steroids into Ring-A-Aromatized Steroids and 19-Norsteroids involving a Regioselective β-Scission of Alkoxyl Radicals; Synthesis of Two Marine Natural Products, 19-Nor-5α-cholestan-3β-ol and 19-norcholest-4-en-3-one...
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A new transformation of steroids into 19-norsteroids and ring-A-aromatized steroids is described.The transformation method involves the removal of the 10β-methyl group by a regioselective β-scission of alkoxyl radicals.Cholesterol was transformed into two marine natural products, 19-nor-5α-cholestan-3β-ol and 19-norcholest-4-en-3-one, and into 19-norcholesta-1,3,5(10)-trien-3-ol.Transformations of 3β-hydroxyandrost-5-en-17-one into 19-nortestosterone, estrone, and the related estranes are also described.
- Suginome, Hiroshi,Senboku, Hisanori,Yamada, Shinji
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p. 2199 - 2205
(2007/10/02)
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- Interactions of Thiol-Containing Androgens with Human Placental Aromatase
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A series of thiol androgens were synthesized and investigated to characterize structural features important for the inhibition of aromatase.Analogues of androstenedione with thiol groups in either the 2α-, 10β-, or 19-positions caused time-dependent inhibition of human placental aromatase.When their KI and kcat values were compared with those of 4-hydroxyandrost-4-ene-3,17-dione (4-OHa) and 10-β-propargylestr-4-ene-3,17-dione (PED), the thiol androgen 10β-mercaptoestr-4-ene-3,17-dione (10β-SHnorA) proved to be the most potent suicide substrate.However, 19-merc aptoandrost-4-ene-3,17-dione (19-SHA) was the best all-around inhibitor.All compounds except 19-SHA exhibited normal type I P-450 difference spectra with partially purified/solubilized, human placental aromatase.The KS values for the series of compounds compared qualitatively to the KI values determined from the time and concentration-dependent inhibition experiments. 19-SHA induced split Soret peaks at 380 and 474 nm, which suggested binding of the 19-thiolate directly to the ferric iron of aromatase.This binding could be displaced by aminoglutethimide but not by androstenedione.The inhibitory activity of 19-SHA may be explained by two independent mechanisms: (1) suicide inactivation of aromatase in the ferrous state; and (2) a direct "hyper-type II" binding to the remaining portion of the cytochrome in the ferric state.A free thiol group was necessary for the suicide inhibitory activity of 19-SHA; time-dependent inactivation of aromatase by 19-(acetylthio)androst-4-ene-3,17-dione (19-SAcA) and 19-xanthogenylandrost-4-ene-3,17-dione (19-XanA) could be prevented if the microsomes were preincubated with a carboxyesterase inhibitor.Aromatase previously inactivated by either thiol androgens, 4-OHA, or PED could not be reactivated after incubation with the disulfide reducing agent dithiothreitol, which suggests that a disulfide bond may not be involved in aromatase inactivation by these inhibitors.
- Bednarski, Patrick J.,Nelson, Sidney D.
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p. 203 - 213
(2007/10/02)
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- A New Synthesis of 19-Nor Steroids via 2,4-Dibromoestrogens
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19-Nor steroids (7) and (8) have been synthesised via oxidation of 2,4-dibromoestrogens (1) and (2) with nitric acid followed by hydrogenation over palladium-on-charcoal and subsequent treatment with Nafion-H.
- Numazawa, Mitsuteru,Hoshi, Kumiko,Kimura, Katsuhiko
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p. 490 - 491
(2007/10/02)
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- Unusual Enolizations in 19-Nor-3-ketosteroids
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The direction of enolization of 19-nor-3-ketosteroids was found to proceed predominantly towards C-2 irrespective of the ring junction at C-5.
- Abul-Hajj, Yusuf J.
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p. 1479 - 1481
(2007/10/02)
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- LONG-ACTING CONTRACEPTIVE AGENTS: FURYLALKYLCARBOXYLIC ACID ESTERS OF NORETHISTERONE
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5-Methyl- and 5-ethylfurylalkylcarboxylic esters of norethisterone (17α-ethynyl-17β-hydroxyestr-4-en-3-one) were prepared in high yield in the presence of thallous ethoxide.The activities of these compounds as long-acting contraceptive agents have been evaluated.
- Wan, A. S. C.,Ngiam, T. L.,Leung, S. L.,Go, M. L.,Kielczewski, M.,et al.
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p. 321 - 326
(2007/10/02)
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- ESTERIFICATION OF ACID CHLORIDES WITH THALLIUM AND POTASSIUM SALTS OF 19-NORETHISTERONE: FORMATION OF 17-ENOL ESTERS
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During the esterification of acid chlorides with thallium and potassium salts of 19-norethisterone, 17-enol esters were isolated.The enol esters are formed via the intermediate, 4-estrene-3,17-dione.
- Herz, Josef E.,Gunatilaka, A. A. Leslie,Sotheeswaran, Subramaniam,Torres, J. V.
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p. 261 - 266
(2007/10/02)
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- A SHORT EFFICIENT SYNTHESIS OF 19-NORANDROST-4-ENE-3,17-DIONE
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A three-step conversion of 3aα-H-4α-(3'-propionic acid)-7aβ-methylhexahydro-1,5-indanedione into 19-norandrost-4-ene-3,17-dione is described.
- Cooper, Gary F.,Van Horn, Albert R.
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p. 1479 - 1482
(2007/10/02)
-
- Microbiological Transformations. XIII. Transformations of 19-Nor and 19-Hydroxy Analogues of Testosterone and Androstendione by Means of Rhodotorula mucilaginosa Strain
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Preparative transformation carried out
- Dmochowska-Gladysz, Jadwiga,Tlomak, Elzbieta,Siewinski, Antoni
-
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- Process for the preparation of 13β-alkyl-4-gonene-3,17-diones
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Novel process for the preparation of 13β-alkyl-4-gonene-3,17-diones of the formula STR1 wherein R1 is methyl or ethyl, consists of REACTING A 7Aβ-ALKYL,5,6,7,7A-TETRAHYDROINDANE-1,5-DIONE WITH FORMALDEHYDE AND AN ARYLSULFINIC ACID OR AN ADDUCT OF FORMALDEHYDE AND ARYLSULFINIC ACID TO PRODUCE A TETRAHYDROINDANE DERIVATIVE; Hydrogenating the tetrahydroindane derivative with hydrogen in the presence of a palladium-, platinum-, or rhodium-containing hydrogenation catalyst to produce a perhydroindane derivative; Condensing the perhydroindane derivative in the presence of a proton-accepting agent with a 7,7-alkylenedioxy-3-oxooctanoic acid ester; Treating the product obtained with a strong aqueous base and then heating the product in an inert solvent to produce a 4,5-secosteroid; Hydrogenating the 4,5-secosteroid in the presence of a palladium-, platinum-, rhodium-, or nickel-containing hydrogenation catalyst; and Hydrolyzing and cyclizing the hydrogenated 4,5-secosteroid by treatment with a strong acid.
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- Tetrahydropyran-2-ols
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Stereo-specific total synthesis of steroidal materials. 7-Substituted 3-oxo-1-heptenes or variants thereof are reacted with 2-alkylcycloalkane-1,3-diones yielding 3-substituted 6a β-alkyl-cyclopenta [f] [1] benzopyrans or naphtho [2,1-b] pyrans. These are then subjected to a selective catalytic hydrogenation followed by an introduction of a hydroxy, alkoxy or acyloxy group at the 4a-position to produce a 3-substituted 6a β,4a-hydroxy, alkoxy or acyloxy perhydrocyclopenta [f] [1] benzopyran or perhydro-naphtho [2,1-b] pyran. These latter compounds are then converted into 4- or 5-(3-oxoalkyl)perhydroindene-5-ones or perhydronaphthalene-6-ones which in turn can be converted to known steroidal materials by known methods.
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- Aryl ketals of 1-chloro-4-oxo-pentane
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The intermediates and processes of this disclosure provide a new stereo-specific total synthesis of steroidal materials having known valuable pharmacological properties. A fundamental feature of this disclosure is the utilization of aryl ketals, preferably phenylenedioxy ketals derived from catechol as protective groups for oxo moieties in the polycyclic intermediates used in the aforesaid total snythesis.
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- 6-(3-Cyanopropyl)-2-vinyl tetrahydropyran-2-ol and its tautomer
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A multi-step, stereospecific total synthesis of steroids utilizing intermediates having a cyanoalkyl A-ring precursor is disclosed. The initial starting materials for this process are the relatively inexpensive and commercially available reagents γ-butyrolactone and sodium cyanide. The process is suitable for the preparation of racemic or optically active, medicinally valuable steroids, particularly 19-norsteroids. It is a feature of this process that conditions employed during the multiple step synthesis are selected so as to retain the normally labile nitrile group even during hydrogenation and hydrolysis steps. In this manner, it is possible to employ the nitrile group as an A-ring precursor without resorting the protective groups as was heretofore found necessary in previous steroid total synthesis processes.
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- Steroid total synthesis process utilizing a cyanoalkyl A-ring precursor
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A multi-step, stereospecific total synthesis of steroids utilizing intermediates having a cyanoalkyl A-ring precursor is disclosed. The initial starting materials for this process are the relatively inexpensive and commercially available reagents γ-butyrolactone and sodium cyanide. The process is suitable for the preparation of racemic or optically active, medicinally valuable steroids, particularly 19-norsteroids. It is a feature of this process that conditions employed during the multiple step synthesis are selected so as to retain the normally labile nitrile group even during hydrogenation and hydrolysis steps. In this manner, it is possible to employ the nitrile group as an A-ring precursor without resorting to protective groups as was heretofore found necessary in previous steroid total synthesis processes.
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