979-02-2Relevant articles and documents
Crystal structure of 3β-acetoxy-pregna-5,16-dien-20-one (16 DPA)
Bandhoria, Pankaj,Gupta, Vivek K.,Gupta,Jain,Varghese
, p. 161 - 166 (2006)
The title compound, 3β-acetoxy-pregna-5,16-dien-20-one, C 23H32O3, has been synthesized by acetylation followed by oxidation of diosgenin and its crystal structure has been solved from single crystal X-ray diffraction data. The compound crystallizes into orthorhombic space group P212121 with unit cell parameters: a = 6.031(4) A, b = 12.481(2) A, c = 27.162(5) A, Z = 4. The crystal structure has been refined to R = 0.0597 for 1291 observed reflections. Rings A and C of the compound are in chair conformation whereas ring B is in half-chair conformation. Ring D is in envelop conformation. The A/B ring junction is quasi-trans, while ring systems B/C and C/D are trans fused about the C8-C9 and C13-C14 bonds, respectively. The steroid nucleus has a small twist, as shown by the C19-C10...C13-C18 pseudo-torsion angle of 9.5°. The crystal packing is determined by a pair of weak C-H...O hydrogen bonds in addition to van der Waals interactions.
Synthesis of silyl enol and silyl dienol ethers of 20-Oxosteroids: The effect of β-substituents
Moreno, Maria Jose S. M.,Martins, Rosa Maria L. M.,Sa E Melo, Maria Luisa,Campos Neves, Andre S.
, p. 529 - 530 (1997)
An efficient method to obtain regioselectively the title compounds is described. Experimental studies concerning the effect of β-substituents on the generation of β-substituted silyl enol ethers made feasible for the first time the isolation and identification of the products resulting from the unstable thermodynamic silyl enol ether.
Facile green synthesis of 16-dehydropregnenolone acetate (16-DPA) from diosgenin
Baruah, Diganta,Das, Ram Nath,Konwar, Dilip
, p. 79 - 84 (2016)
Chromium- and MnO2-free green synthesis of industrially important steroidal drug intermediate 16-dehydropregnenolone acetate (16-DPA) starting from diosgenin is reported. The reaction sequence involves three steps: acetolysis followed by acetylation, oxidation, and hydrolysis. In the first step, Ac2O was used both as reagent and solvent in combination with a Lewis acid (AlCl3), which led to considerable reduction of high temperature and pressure requirements of earlier processes. The oxidation step was made catalytic with the use of KMnO4(5 mol%) in the presence of co-oxidant NaIO4, leading to less waste generation (of chromium, MnO2, etc.). Minimization of the temperature, pressure, time consumption, and use of nontoxic solvents makes the process very handy and simple.
A Dual Role Reductase from Phytosterols Catabolism Enables the Efficient Production of Valuable Steroid Precursors
Peng, Haidong,Wang, Yaya,Jiang, Kai,Chen, Xinru,Zhang, Wenlu,Zhang, Yanan,Deng, Zixin,Qu, Xudong
supporting information, p. 5414 - 5420 (2021/02/05)
4-Androstenedione (4-AD) and progesterone (PG) are two of the most important precursors for synthesis of steroid drugs, however their current manufacturing processes suffer from low efficiency and severe environmental issues. In this study, we decipher a dual-role reductase (mnOpccR) in the phytosterols catabolism, which engages in two different metabolic branches to produce the key intermediate 20-hydroxymethyl pregn-4-ene-3-one (4-HBC) through a 4-e reduction of 3-oxo-4-pregnene-20-carboxyl-CoA (3-OPC-CoA) and 2-e reduction of 3-oxo-4-pregnene-20-carboxyl aldehyde (3-OPA), respectively. Inactivation or overexpression of mnOpccR in the Mycobacterium neoaurum can achieve exclusive production of either 4-AD or 4-HBC from phytosterols. By utilizing a two-step synthesis, 4-HBC can be efficiently converted into PG in a scalable manner (100 gram scale). This study deciphers a pivotal biosynthetic mechanism of phytosterol catabolism and provides very efficient production routes of 4-AD and PG.
Continuous Flow Synthesis of 16-Dehydropregnenolone Acetate, a Key Synthon for Natural Steroids and Drugs
Mancino, Valentina,Cerra, Bruno,Piccinno, Alessandro,Gioiello, Antimo
supporting information, p. 600 - 607 (2018/05/14)
A telescoped multistep process to provide the continuous delivery of 16-dehydropregnenolone acetate (16-DPA) from diosgenin is described. The method was evaluated through batch screenings that helped to identify critical bottlenecks and flowability, and the best conditions were optimized in flow systems before the individual steps were telescoped together into a single integrated flow process. Further highlights of our approach include the use of efficient in-line extraction operations and reaction monitoring, the avoidance of time-consuming purifications between steps, and improvement of efficiency and safety standards.
Some observations on solasodine reactivity
Jastrzebska, Izabella,Morzycki, Jacek W.
, p. 13 - 17 (2017/09/15)
This article presents new transformations of solasodine – a representative steroid alkaloid sapogenin from the Solanum family. Oxidation of N,O-diacetylated solasodine with either NaNO2/BF3·Et2O or t-BuONO/BF3·Et2O resulted in partial degradation of the side chain to (20S)-3β-acetoxypregn-5-ene-20,16β-carbolactone (vespertilin acetate). The same starting compound when treated with TMSOTf afforded the corresponding pseudosapogenin after aqueous work-up. However, when the crude reaction mixture was directly subjected to purification on a silica gel column, efficient autoxidation to pregna-5,16-dien-3β-ol-20-one acetate was observed. One-step synthesis of this important drug intermediate from spirosolan alkaloids may be potentially exploited for large-scale production of steroid hormones.
METHODS FOR PREPARATION OF BILE ACIDS AND DERIVATIVES THEREOF
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Page/Page column 56, (2017/02/24)
The present application relates to a method of preparing compounds of Formula (I) or a pharmaceutically acceptable salt, solvate, or amino acid conjugate thereof, R1 is H, α-OH, β-ΟΗ, or an oxo group.
Microwave-assisted stereoselective approach to novel steroidal ring D-fused 2-pyrazolines and an evaluation of their cell-growth inhibitory effects in vitro
Mótyán, Gergo,Kovács, Ferenc,W?lfling, János,Gyovai, András,Zupkó, István,Frank, éva
, p. 36 - 46 (2016/05/24)
Novel ring D-condensed 2-pyrazolines in the Δ5-androstene series were efficiently synthesized from 16-dehydropregnenolone or its acetate with different arylhydrazines or methylhydrazine, respectively, under microwave irradiation. The reactions are assumed to occur via hydrazone intermediates, followed by intramolecular 1,4-addition leading to the fused heteroring stereoselectively with a 16α,17α-cis ring junction. The synthesized compounds were subjected to in vitro pharmacological studies of their antiproliferative activities against four human breast (MCF7, T47D, MDA-MB-231 and MDA-MB-361) and three cervical (HeLa, C33A and SiHA) malignant cell lines. Flow cytometry revealed that the most potent agent elicited a cell cycle disturbance.
Synthesis of steroidal derivatives containing substituted, fused and spiro pyrazolines
Romero-López, Anabel,Montiel-Smith, Sara,Meza-Reyes, Socorro,Merino-Montiel, Penélope,Vega-Baez, José Luis
, p. 86 - 92 (2014/07/08)
An efficient and facile synthesis of fused, substituted and spiro pyrazoline steroid derivatives through a cycloaddition reaction of different α,β-unsaturated ketones with hydrazine acetate in acetic acid is reported. Depending on the starting material, the ring closure reaction provided a mixture of two steroidal pyrazoline epimers that were separated and studied by NMR techniques. In one case it was possible to isolate and characterize the hydrazone derivative as the reaction intermediate, which confirms the mechanism proposed in the literature [11,25,26].2014 Published by Elsevier Inc.
Synthesis and characterization of new phenyl esters derived from 16-dehydropregnenolone acetate (16-DPA)
Li, Hongqi,Fang, Jueshu,Li, Juan,Wang, Yulong,Tian, Xiujuan,Xiang, Yuanhui
, p. 3887 - 3893 (2013/10/22)
A series of new phenyl esters based on a 5,16-pregnadiene-20-one skeleton, namely 3β-benzoyloxy-5,16-pregnadiene-20-ones, which may be good inhibitors of 17α-hydroxylase and 5α-reductase enzyme or useful intermediates for producing steroidal drugs, were synthesized starting from diosgenin. The structures of the steroids were characterized by 1H nuclear magnetic resonance (NMR), 13C NMR, infrared (IR), and mass spectra.
