2283-82-1

Usage

Uses

Dehydro Androsterone is an Androsterone (A637535) analogue.

InChI:InChI=1/C19H28O2/c1-18-9-7-13(20)11-12(18)3-4-14-15-5-6-17(21)19(15,2)10-8-16(14)18/h3,13-16,20H,4-11H2,1-2H3/t13-,14+,15+,16+,18+,19+/m1/s1

Synthetic route

(3R,8R,9S,10R,13S,14S)-10,13-dimethyl-17-oxo-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yl acetate (5223-99-4) → 3α-hydroxy-androst-5-en-17-one (2283-82-1)

Conditions	Yield
With methanol; sodium hydroxide at 40℃; for 4h; Inert atmosphere;	95.8%
With potassium hydroxide In methanol for 1h; Heating;	1.9 g

17,17-ethylenedioxy-androst-5-ene-3α-ol (14456-21-4) → 3α-hydroxy-androst-5-en-17-one (2283-82-1)

Conditions	Yield
With hydrogenchloride	80%
With hydrogenchloride In ethanol; water for 5h; Reflux;

dehydroepiandrosterone p-nitrobenzoate (1383292-25-8) → 3α-hydroxy-androst-5-en-17-one (2283-82-1)

Conditions	Yield
With potassium hydroxide In methanol; water for 1h; Sonication;	72%
With NaOH In tetrahydrofuran; methanol; water

5-androstenedione (571-36-8) → dehydroepiandrosterone (53-43-0) + 3α-hydroxy-androst-5-en-17-one (2283-82-1)

Conditions	Yield
With ethanol; nickel Hydrogenation;

3β-tosyloxyandrost-5-ene-17-one (2719-96-2) → 3α-hydroxy-androst-5-en-17-one (2283-82-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: 3.2 g / various solvent(s) / 4 h / 160 °C 2: 1.9 g / aq. KOH / methanol / 1 h / Heating View Scheme
Multi-step reaction with 2 steps 1: 3.2 g / tetra-n-butylammonium acetate / various solvent(s) / 4 h / 160 °C 2: 1.9 g / aq. KOH / methanol / 1 h / Heating View Scheme

3β-acetoxy-5α,6α-epoxy-androst-17-one, ethylene ketal (115350-45-3) → 3α-hydroxy-androst-5-en-17-one (2283-82-1)

Conditions	Yield
Multi-step reaction with 5 steps 1: lithium aluminium tetrahydride 2: pyridine 3: N,N-dimethyl-aniline 4: potassium hydroxide 5: hydrogenchloride View Scheme
Multi-step reaction with 5 steps 1: lithium aluminium tetrahydride / tetrahydrofuran / 3 h / 35 °C / Reflux 2: pyridine / dichloromethane / 16 h / 10 - 20 °C / Cooling with ice 3: N,N-dimethyl-aniline / chloroform / 5 h / Reflux 4: potassium hydroxide; water / methanol / 1 h / Reflux 5: hydrogenchloride / ethanol; water / 5 h / Reflux View Scheme

17,17-ethylenedioxy-androstane-3β,5α-diol → 3α-hydroxy-androst-5-en-17-one (2283-82-1)

Conditions	Yield
Multi-step reaction with 4 steps 1: pyridine 2: N,N-dimethyl-aniline 3: potassium hydroxide 4: hydrogenchloride View Scheme
Multi-step reaction with 4 steps 1: pyridine / dichloromethane / 16 h / 10 - 20 °C / Cooling with ice 2: N,N-dimethyl-aniline / chloroform / 5 h / Reflux 3: potassium hydroxide; water / methanol / 1 h / Reflux 4: hydrogenchloride / ethanol; water / 5 h / Reflux View Scheme

17,17-ethylenedioxy-3β-methanesulfonyloxy-androstane-5α-ol (15577-68-1) → 3α-hydroxy-androst-5-en-17-one (2283-82-1)

Conditions	Yield
Multi-step reaction with 3 steps 1: N,N-dimethyl-aniline 2: potassium hydroxide 3: hydrogenchloride View Scheme
Multi-step reaction with 3 steps 1: N,N-dimethyl-aniline / chloroform / 5 h / Reflux 2: potassium hydroxide; water / methanol / 1 h / Reflux 3: hydrogenchloride / ethanol; water / 5 h / Reflux View Scheme

5-androsten-3α-ol-17-one acetate 17-ethylene ketal (14456-20-3) → 3α-hydroxy-androst-5-en-17-one (2283-82-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: potassium hydroxide 2: hydrogenchloride View Scheme
Multi-step reaction with 2 steps 1: potassium hydroxide; water / methanol / 1 h / Reflux 2: hydrogenchloride / ethanol; water / 5 h / Reflux View Scheme

prasterone acetate → 3α-hydroxy-androst-5-en-17-one (2283-82-1)

Conditions	Yield
Multi-step reaction with 7 steps 1: p-toluenesulfonic acid monohydrate 2: 3-chloro-benzenecarboperoxoic acid 3: lithium aluminium tetrahydride 4: pyridine 5: N,N-dimethyl-aniline 6: potassium hydroxide 7: hydrogenchloride View Scheme
Multi-step reaction with 7 steps 1: orthoformic acid triethyl ester / toluene-4-sulfonic acid / 3 h / Inert atmosphere; Reflux 2: 3-chloro-benzenecarboperoxoic acid / dichloromethane / -5 - 20 °C 3: lithium aluminium tetrahydride / tetrahydrofuran / 3 h / 35 °C / Reflux 4: pyridine / dichloromethane / 16 h / 10 - 20 °C / Cooling with ice 5: N,N-dimethyl-aniline / chloroform / 5 h / Reflux 6: potassium hydroxide; water / methanol / 1 h / Reflux 7: hydrogenchloride / ethanol; water / 5 h / Reflux View Scheme

→ 3α-hydroxy-androst-5-en-17-one

Conditions	Yield
Multi-step reaction with 6 steps 1: 3-chloro-benzenecarboperoxoic acid 2: lithium aluminium tetrahydride 3: pyridine 4: N,N-dimethyl-aniline 5: potassium hydroxide 6: hydrogenchloride View Scheme
Multi-step reaction with 6 steps 1: 3-chloro-benzenecarboperoxoic acid / dichloromethane / -5 - 20 °C 2: lithium aluminium tetrahydride / tetrahydrofuran / 3 h / 35 °C / Reflux 3: pyridine / dichloromethane / 16 h / 10 - 20 °C / Cooling with ice 4: N,N-dimethyl-aniline / chloroform / 5 h / Reflux 5: potassium hydroxide; water / methanol / 1 h / Reflux 6: hydrogenchloride / ethanol; water / 5 h / Reflux View Scheme

Androstenedione (63-05-8) → 3α-hydroxy-androst-5-en-17-one (2283-82-1)

Conditions	Yield
Multi-step reaction with 4 steps 1.1: potassium tert-butylate / tert-butyl alcohol / 1 h / 30 - 35 °C / Inert atmosphere 1.3: 65 h / 45 °C / pH 6.5 / Enzymatic reaction 2.1: D-glucose; NAD; glucose dehydrogenase (CDX-901)_; ketoreductase from Sphingomonas wittichii; potassium carbonate / ethyl acetate; aq. phosphate buffer / 21 h / 32.5 °C / pH 6.3 - 6.5 / Inert atmosphere; Enzymatic reaction 3.1: triphenylphosphine; di-isopropyl azodicarboxylate / tetrahydrofuran / 5 - 20 °C / Inert atmosphere 4.1: potassium hydroxide / water; methanol / 1 h / Sonication View Scheme
Multi-step reaction with 4 steps 1: potassium tert-butylate / tert-butyl alcohol / 1 h / 30 - 35 °C / Inert atmosphere 2: D-glucose; NAD; glucose dehydrogenase (CDX-901)_; ketoreductase from Sphingomonas wittichii; potassium carbonate / ethyl acetate; aq. phosphate buffer / 21 h / 32.5 °C / pH 6.3 - 6.5 / Inert atmosphere; Enzymatic reaction 3: triphenylphosphine; di-isopropyl azodicarboxylate / tetrahydrofuran / 5 - 20 °C / Inert atmosphere 4: potassium hydroxide / water; methanol / 1 h / Sonication View Scheme

dehydroepiandrosterone (53-43-0) → 3α-hydroxy-androst-5-en-17-one (2283-82-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: triphenylphosphine; di-isopropyl azodicarboxylate / tetrahydrofuran / 5 - 20 °C / Inert atmosphere 2: potassium hydroxide / water; methanol / 1 h / Sonication View Scheme

5-androstenedione (571-36-8) → 3α-hydroxy-androst-5-en-17-one (2283-82-1)

Conditions

Yield

Multi-step reaction with 3 steps 1: D-glucose; NAD; glucose dehydrogenase (CDX-901)_; ketoreductase from Sphingomonas wittichii; potassium carbonate / ethyl acetate; aq. phosphate buffer / 21 h / 32.5 °C / pH 6.3 - 6.5 / Inert atmosphere; Enzymatic reaction 2: triphenylphosphine; di-isopropyl azodicarboxylate / tetrahydrofuran / 5 - 20 °C / Inert atmosphere 3: potassium hydroxide / water; methanol / 1 h / Sonication View Scheme

Upstream product

• 53-41-8 cis-androsterone 
• 571-36-8 5-androstenedione 
• 5223-99-4 (3R,8R,9S,10R,13S,14S)-10,13-dimethyl-17-oxo-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yl acetate 
• 853-23-6 prasterone acetate 
• 14456-20-3 3β-acetoxy-5-androsten-17-one-17-ethyleneketal 
• 63-05-8 Androstenedione 
• 53-43-0 dehydroepiandrosterone 
• 1383292-25-8 dehydroepiandrosterone p-nitrobenzoate 
• 14456-21-4 17,17-ethylenedioxy-androst-5-ene-3α-ol 
• 14456-20-3 5-androsten-3α-ol-17-one acetate 17-ethylene ketal 
• 15577-68-1 17,17-ethylenedioxy-3β-methanesulfonyloxy-androstane-5α-ol 
• 13262-99-2 17,17-ethylenedioxy-androstane-3β,5α-diol 
• 115350-45-3 3β-acetoxy-5α,6α-epoxy-androst-17-one, ethylene ketal 
• 2719-96-2 3β-tosyloxyandrost-5-ene-17-one 

Downstream Products

• 5419-51-2 3β-(2-tetrahydropyranyloxy)-5-androstene-17β-0l 
• 566-19-8 3β-hydroxyandrost-5-ene-7,17-dione 
• 628-13-7 pyridine hydrochloride 
• 521-17-5 androst-5-ene-3β,17β-diol 
• 63015-10-1 3β-Hydroxy-17-hydrazono-androsten-(5) 
• 853-23-6 3β-acetoxy-5-androsten-17-one 
• 571-36-8 3,17-Dioxo-androsten-5 
• 63-05-8 (8R,9S,10R,13S)-10,13-dimethyl-7,8,9,10,11,12,13,14,15,16-decahydro-1H-cyclopenta[a]phenanthrene-3,17(2H,6H)-dione 
• 16895-59-3 androst-5-ene-3α,17β-diol 
• 14167-51-2 5-androstene-3α,16α-diol-17-one 
• 853-23-6 prasterone acetate 
• 53-43-0 dehydroepiandrosterone 
• 63-05-8 Androstenedione 
• 3747-91-9 3α-(trimethylsilyoxy)androst-5-en-17-one 

Relevant academic research and scientific papers

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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.

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Development of a Chemoenzymatic Process for Dehydroepiandrosterone Acetate Synthesis

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