74644-60-3

Upstream product

• 53-43-0 dehydroepiandrosterone 
• 1093-91-0 3β-hydroxy-16α-bromoandrost-5-ene-17-one 
• 53-43-0 dehydroepiandrosterone 
• 50-00-0 formaldehyd 
• 24335-49-7 3β-acetoxy-16α-bromoandrost-5-en-17-one 
• 111293-55-1 3-acetoxy-16-bromo-androst-5-en-17-ol 
• 24335-50-0 3β-acetoxy-16β-bromo-androst-5-en-17-one 
• 102813-25-2 3β-acetoxy-16β-bromo-17-hydroxy-pregn-5-en-20-one oxime 

Downstream Products

• 1232-73-1 16α-hydroxy dehydroepiandrosterone 
• 1093-91-0 3β-hydroxy-16α-bromoandrost-5-ene-17-one 
• 1159-66-6 (R)-3,17-Dihydroxy-10,13-dimethyl-1,2,3,4,7,8,9,10,11,12,13,14,15,17-tetradecahydro-cyclopenta[a]phenanthren-16-one 
• 133522-45-9 14β-androst-5-ene-3β,17α-diyl 3-acetate 17-p-toluenesulfonate 
• 53-43-0 3β-hydroxy-14β-androst-5-en-17-one 

Relevant academic research and scientific papers

Synthesis and biological evaluation of 3β-androsta-5,8(14),15-trien-17-one derivatives as potential anticancer agents

A novel and operationally simple method for highly efficient synthesis of promising anti-cancer 3β-hydroxy-16-arylandrosta-5,8(14),15-trien-17-ones was reported. Compounds were tested for their cytotoxic activities against A549, SKOV3, MKN-45 and MDA-MB-4

Darzens reaction rate enhancement using aqueous media leading to a high level of kinetically controlled diastereoselective synthesis of steroidal epoxyketones

Darzens reactions between halocarbonyls and aldehydes have been carried out in water in the presence of a Li+-containing base, a phase-transfer catalyst, and granular polytetrafluoroethylene under mechanical stirring. Reactions using both aromatic and aliphatic aldehydes produced epoxides stereoselectively in good to excellent yields. This is the first time that aliphatic aldehydes with α-H have been used in aqueous Darzens reactions. The Darzens reactions were much faster in water than in organic solvents. This aqueous rate enhancement occurred for Darzens reactions between enantiopure steroidal haloketones and aldehydes, yielding enantiopure spiroepoxides with a high level of kinetically controlled diastereoselectivity. Chromatography was avoided in the purifications of the steroidal spiroepoxides. This is an example of preparing enantiopure epoxyketones via aqueous Darzens reaction using chiral α-haloketone substrates.

Stereoselective hydrolysis of 16α-halo-17-keto steroids and long-range substitution effects on the hydrolysis of 16α-bromo-17-ketones and 2α-bromo-3-ketones

Epimerization of 16α-chloro- (1a), bromo- (1b), and iodo-3β-hydroxy-5-androsten-17-one (1c) by a brief treatment with 0.2 equiv NaOH in aqueous pyridine reached equilibrium between 16α- and 16β-halo ketones. 16α-/16β-Halo ketone ratios at equilibrium were 1.5 for Cl, 1.25 for Br, and 1.0 for I. Kinetic analysis showed that compounds 1a-c were stereoselectively converted to the corresponding 16α-hydroxy derivative 3 by an S(N)2 mechanism, in which the order of the apparent reactivity was Br > I > Cl. The hydrolysis of a number of 16α-bromo-17-ketones and 2α-bromo-3-ketones was carried out. The yields of the corresponding alcohols were found to depend on remote structural features in the steroids.

Stereospecific Synthesis of 16α-Hydroxy-17-oxo Steroids by Controlled Alkaline Hydrolysis of Corresponding 16-Bromo 17-Ketones and Its Reaction Mechanism

Synthesis of 16α-hydroxy-17-oxo steroids 3, 5b, and 3β,16α-dihydroxy-5-17-oxoandrosten-3-yl sulfate (7) from 16α-bromo-17-oxo steroids 1, 5a, and 6a and the reaction mechanism of the controlled alkaline hydrolysis are described.Treatment of the bromo ketones with NaOH in aqueous DMF gave the 16α-hydroxy 17-ketones stereoselectively in 95percent yield without formation of other ketols.The sodium salt of 3-sulfate 7 was also obtained in one step in 85percent yield from the corresponding bromo ketone (1a).Isotope-labeling experiments and time-course studies showed that equilibration between the 16-bromo epimers 1 and 2 precedes the formation of 3, in which the true intermediate is 2 and not 1, and that the ketol 3 is formed by the direct SN2 displacement of the 16β-bromine.The 16β-morpholino derivative 8 obtained by reaction of 1 with morpholine was shown to be an isomerized product of the 16α isomer which is produced also by SN2 displacement of the 16β-bromine.The mechanism of ketol rearrangement of 3 to the 17β-hydroxy-16-oxo compound 4 was found to involve a hydration to the carbonyl function.The new hydration-dehydration mechanism is proposed for the ketol rearrangement.

CONTROLLED ALKALINE HYDROLYSIS OF STEROIDAL α-BROMOKETONES: NEW CONDITIONS AND SYNTHESIS OF 2α-HYDROXY-3-ONES

Controlled alkaline hydrolysis of 16α-bromo-17-keto steroids 1, 5 and 7 with potassium carbonate and tetra-n-butylammonium hydroxide (n-Bu4NOH) and synthesis of 2α-hydroxy-3-ones 11, 13 and 16 by the controlled hydrolysis of the corresponding 2α-bromo-3-ones 9, 12 and 15 are described.Treatment of the bromoketones 1, 5 and 7 with potassium carbonate in aqueous acetone or with n-Bu4NOH in aqueous dimethylformamide (DMF) gave 16α-hydroxy-17-ones 3, 6 and 8 in 85-90percent yield, respectively. 2α-Hydroxy-3-ones 11, 13 and 16 were obtained by hydrolysis of the corresponding bromoketones 9, 12 and 15 in high yields using the above conditions or sodium hydroxide in pyridine or DMF, respectively.Deuterium labeling experiments suggested that equilibration between the 2α-bromoketone 9 and the 2β-bromo isomer 10 precedes the formation of the ketol 11 in which the true intermediate might be the 2β-isomer 10.However, rearranged androstane derivatives, 3β-hydroxy-2-ones 18 and 20, were stereoselectively obtained by treatment of the bromoketones 12 and 15 with an excess amount of sodium hydroxide.