7148-51-8

Basic information

• Product Name: 16,(5-ALPHA)-ANDROSTEN-3-BETA-OL
• Synonyms: 5A-androst-16-en-3B-ol;5Androstan-16-en-3ol;(3,5a)-Androst-16-en-3-ol;3-Hydroxy-5a-androst-16-ene;5a-Androst-16-en-3-ol;JNF 55;NSC 65888;3β-Androstenol
• CAS NO: 7148-51-8
• Molecular Formula: C₁₉H₃₀O
• Molecular Weight: 274.44
• EINECS: 214-573-1
• Product Categories: Intermediates & Fine Chemicals;Metabolites & Impurities;Pharmaceuticals;Steroids
• Mol File: 7148-51-8.mol
• Article Data: 13

Chemical Properties

• Melting Point: 123-124 °C
• Boiling Point: 374.1 °C at 760 mmHg
• Flash Point: 156.5 °C
• Appearance: /
• Density: 1.037 g/cm³
• Vapor Pressure: 4E-07mmHg at 25°C
• Refractive Index: 1.54
• PKA: 14.84±0.60(Predicted)
• CAS DataBase Reference: 16,(5-ALPHA)-ANDROSTEN-3-BETA-OL(CAS DataBase Reference)
• NIST Chemistry Reference: 16,(5-ALPHA)-ANDROSTEN-3-BETA-OL(7148-51-8)
• EPA Substance Registry System: 16,(5-ALPHA)-ANDROSTEN-3-BETA-OL(7148-51-8)

Safety Data

• Hazardous Substances Data: 7148-51-8(Hazardous Substances Data)

Usage

Chemical Properties

White Solid

Uses

A metabolite of 16-Androstene.

InChI:InChI=1/C19H30O/c1-18-9-3-4-16(18)15-6-5-13-12-14(20)7-11-19(13,2)17(15)8-10-18/h3,9,13-17,20H,4-8,10-12H2,1-2H3/t13-,14+,15-,16-,17+,18-,19-/m0/s1

Synthetic route

5α-androst-16-en-3-one (18339-16-7) → 5α-androst-16-en-3β-ol (7148-51-8) + androstenol (3597-54-4, 4572-71-8, 7148-51-8, 14152-27-3, 18485-74-0, 19321-55-2, 64681-01-2, 86335-09-3, 86335-14-0, 86335-15-1, 103615-88-9, 103615-90-3, 1153-51-1)

Conditions	Yield
With sodium tetrahydroborate In tetrahydrofuran; methanol for 2h; Ambient temperature;	A 77% B 2%
With aluminum isopropoxide; isopropyl alcohol Isolierung ueber die in wss. Aethanol schwer loesliche Verbindung mit Digitonin;
With ethanol; water; lithium tri-sec-butyl(hydrido)borate 1.) THF, r.t., 3 h; 2.) -55 deg C; Yield given. Multistep reaction. Yields of byproduct given;

17-iodo-3β-hydroxy-5α-androstan-16-ene (95043-81-5) → 5α-androst-16-en-3β-ol (7148-51-8)

Conditions	Yield
With diethylene glycol monoethyl ether sodium salt In 1,4-dioxane at 100℃; for 92h; Reagent/catalyst; Temperature; Solvent; Inert atmosphere;	75.4%
With ethanol; sodium Heating;
With sodium In ethanol Reflux;

16R-bromopregnane-3S,20S-diol (939496-37-4) → 16S,20S-epoxypregnane-3S-ol + 5α-androst-16-en-3β-ol (7148-51-8)

Conditions	Yield
With potassium tert-butylate In tert-butyl alcohol at 60℃; for 18h;	A 65% B 30%
With potassium tert-butylate In tert-butyl alcohol at 82℃; for 5h;	A 46% B 52%

Epiandrosterone (481-29-8) → 5α-androst-16-en-3β-ol (7148-51-8)

Conditions	Yield
Stage #1: Epiandrosterone With toluene-4-sulfonic acid hydrazide In ethanol for 2h; Bamford-Stevens Decomposition; Reflux; Stage #2: With methyllithium In diethyl ether at 22℃; for 16.5h; Bamford-Stevens Decomposition;	29%

5α-androst-16-en-3-one (18339-16-7) → 5α-androst-16-en-3β-ol (7148-51-8)

Conditions	Yield
With lithium aluminium tetrahydride; diethyl ether

5α-androst-16-en-3-one (18339-16-7) + aluminum isopropoxide (555-31-7) + isopropyl alcohol (67-63-0) → 5α-androst-16-en-3β-ol (7148-51-8) + androstenol (3597-54-4, 4572-71-8, 7148-51-8, 14152-27-3, 18485-74-0, 19321-55-2, 64681-01-2, 86335-09-3, 86335-14-0, 86335-15-1, 103615-88-9, 103615-90-3, 1153-51-1)

5α-androst-16-en-3β-yl acetate (72203-76-0) → 5α-androst-16-en-3β-ol (7148-51-8)

Conditions	Yield
With potassium hydroxide In methanol

17-bromo-3β-hydroxy-5α-androstan-16-ene (94438-53-6) → 5α-androst-16-en-3β-ol (7148-51-8)

Conditions	Yield
With ethanol; sodium Heating;

17-chloro-3β-hydroxy-5α-androstan-16-ene (17320-46-6) → 5α-androst-16-en-3β-ol (7148-51-8)

Conditions	Yield
With sodium amide In diethyl ether
With ethanol; sodium
With ethanol; sodium Heating;

Stanolone (521-18-6) → 5α-androst-16-en-3β-ol (7148-51-8)

Conditions	Yield
Multi-step reaction with 3 steps 1: 92 percent / pyridine / 24 h / 0 °C 2: 87 percent / toluene / 480 °C 3: 1.) lithium tris(1,2-dimethylpropyl)hydridoborate; 2.) water, ethanol / 1.) THF, r.t., 3 h; 2.) -55 deg C View Scheme

17β-methoxycarbonyloxy-5α-androstan-3-one (19291-29-3) → 5α-androst-16-en-3β-ol (7148-51-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: 87 percent / toluene / 480 °C 2: 1.) lithium tris(1,2-dimethylpropyl)hydridoborate; 2.) water, ethanol / 1.) THF, r.t., 3 h; 2.) -55 deg C View Scheme

3β-acetoxy-5α-androstan-17-one (1239-31-2) → 5α-androst-16-en-3β-ol (7148-51-8)

Conditions	Yield
Multi-step reaction with 5 steps 1: 2.4 g / hydroxylamine hydrochloride / pyridine / 3 h / 60 °C 2: 0.68 g / sodium nitrite, acetic acid / CH2Cl2 / 1 h / Ambient temperature 3: 75 percent / sodium borohydride / ethanol / 1.5 h / Ambient temperature 4: 0.41 g / pyridine / 12 h / Ambient temperature 5: 2percent potassium hydroxide / methanol View Scheme
Multi-step reaction with 5 steps 1: 2.4 g / hydroxylamine hydrochloride / pyridine / 3 h / 60 °C 2: 0.68 g / sodium nitrite, acetic acid / CH2Cl2 / 1 h / Ambient temperature 3: 75 percent / sodium borohydride / ethanol / 1.5 h / Ambient temperature 4: 0.41 g / pyridine, acetic anhydride / 12 h / Ambient temperature 5: 2percent potassium hydroxide / methanol View Scheme
Multi-step reaction with 5 steps 1: 2.4 g / hydroxylamine hydrochloride / pyridine / 3 h / 60 °C 2: 0.68 g / sodium nitrite, acetic acid / CH2Cl2 / 1 h / Ambient temperature 3: 75 percent / sodium borohydride / ethanol / 1.5 h / Ambient temperature 4: 0.41 g / pyridine, acetic anhydride / 12 h / Ambient temperature 5: 2percent potassium hydroxide / methanol View Scheme

17-nitroimino-5α-androstan-3β-yl acetate (86270-19-1) → 5α-androst-16-en-3β-ol (7148-51-8)

Conditions	Yield
Multi-step reaction with 3 steps 1: 75 percent / sodium borohydride / ethanol / 1.5 h / Ambient temperature 2: 0.41 g / pyridine / 12 h / Ambient temperature 3: 2percent potassium hydroxide / methanol View Scheme
Multi-step reaction with 3 steps 1: 75 percent / sodium borohydride / ethanol / 1.5 h / Ambient temperature 2: 0.41 g / pyridine, acetic anhydride / 12 h / Ambient temperature 3: 2percent potassium hydroxide / methanol View Scheme
Multi-step reaction with 3 steps 1: 75 percent / sodium borohydride / ethanol / 1.5 h / Ambient temperature 2: 0.41 g / pyridine, acetic anhydride / 12 h / Ambient temperature 3: 2percent potassium hydroxide / methanol View Scheme
Multi-step reaction with 3 steps 1: 75 percent / sodium borohydride / ethanol / 1.5 h / Ambient temperature 2: 0.41 g / pyridine, acetic anhydride / 12 h / Ambient temperature 3: 2percent potassium hydroxide / methanol View Scheme

17β-nitroamino-5α-androstan-3β-yl acetate (86270-21-5) → 5α-androst-16-en-3β-ol (7148-51-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: 0.41 g / pyridine / 12 h / Ambient temperature 2: 2percent potassium hydroxide / methanol View Scheme
Multi-step reaction with 2 steps 1: 0.41 g / pyridine, acetic anhydride / 12 h / Ambient temperature 2: 2percent potassium hydroxide / methanol View Scheme
Multi-step reaction with 2 steps 1: 0.41 g / pyridine, acetic anhydride / 12 h / Ambient temperature 2: 2percent potassium hydroxide / methanol View Scheme
Multi-step reaction with 2 steps 1: 0.41 g / pyridine, acetic anhydride / 12 h / Ambient temperature 2: 2percent potassium hydroxide / methanol View Scheme

(3β,5α)-3-(acetyloxy)androstan-17-one 17-oxime (23498-55-7) → 5α-androst-16-en-3β-ol (7148-51-8)

Conditions	Yield
Multi-step reaction with 4 steps 1: 0.68 g / sodium nitrite, acetic acid / CH2Cl2 / 1 h / Ambient temperature 2: 75 percent / sodium borohydride / ethanol / 1.5 h / Ambient temperature 3: 0.41 g / pyridine / 12 h / Ambient temperature 4: 2percent potassium hydroxide / methanol View Scheme
Multi-step reaction with 4 steps 1: 0.68 g / sodium nitrite, acetic acid / CH2Cl2 / 1 h / Ambient temperature 2: 75 percent / sodium borohydride / ethanol / 1.5 h / Ambient temperature 3: 0.41 g / pyridine, acetic anhydride / 12 h / Ambient temperature 4: 2percent potassium hydroxide / methanol View Scheme
Multi-step reaction with 4 steps 1: 0.68 g / sodium nitrite, acetic acid / CH2Cl2 / 1 h / Ambient temperature 2: 75 percent / sodium borohydride / ethanol / 1.5 h / Ambient temperature 3: 0.41 g / pyridine, acetic anhydride / 12 h / Ambient temperature 4: 2percent potassium hydroxide / methanol View Scheme
Multi-step reaction with 4 steps 1: 0.68 g / sodium nitrite, acetic acid / CH2Cl2 / 1 h / Ambient temperature 2: 75 percent / sodium borohydride / ethanol / 1.5 h / Ambient temperature 3: 0.41 g / pyridine, acetic anhydride / 12 h / Ambient temperature 4: 2percent potassium hydroxide / methanol View Scheme

3β-hydroxy-17-hydrozone-5α-androstane (10481-80-8) → 5α-androst-16-en-3β-ol (7148-51-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: N-chloro-succinimide, Py 2: Na, EtOH View Scheme
Multi-step reaction with 2 steps 1: NBS, Py 2: Na, EtOH / Heating View Scheme
Multi-step reaction with 2 steps 1: I2, Et3N 2: Na, EtOH / Heating View Scheme
Multi-step reaction with 2 steps 1: N-chloro-succinimide, Py 2: Na, EtOH / Heating View Scheme

meta-bromotoluene (591-17-3) + 17-bromo-3β-hydroxy-5α-androstan-16-ene (94438-53-6) → 5α-androst-16-en-3β-ol (7148-51-8) + (3β,5α)-17-(3’-methylphenyl)-androst-16-en-3-ol

Conditions	Yield
Stage #1: 17-bromo-3β-hydroxy-5α-androstan-16-ene With tert.-butyl lithium; XPhos In tetrahydrofuran; pentane at -78℃; for 0.5h; Schlenk technique; Inert atmosphere; Stage #2: meta-bromotoluene With tris-(dibenzylideneacetone)dipalladium(0) In tetrahydrofuran; toluene; pentane at -78 - 20℃; Temperature;	A n/a B 44 %Spectr.

2-methylphenyl bromide (95-46-5) + 17-bromo-3β-hydroxy-5α-androstan-16-ene (94438-53-6) → 5α-androst-16-en-3β-ol (7148-51-8) + (3β,5α)-17-(2’-methylphenyl)-androst-16-en-3-ol

Conditions	Yield
Stage #1: 17-bromo-3β-hydroxy-5α-androstan-16-ene With tert.-butyl lithium; XPhos In tetrahydrofuran; pentane at -78℃; for 0.5h; Schlenk technique; Inert atmosphere; Stage #2: 2-methylphenyl bromide With tris-(dibenzylideneacetone)dipalladium(0) In tetrahydrofuran; toluene; pentane at -78 - 20℃;	A n/a B 31 %Spectr.

(4-bromophenoxy)trimethylsilane (17878-44-3) + 17-bromo-3β-hydroxy-5α-androstan-16-ene (94438-53-6) → 5α-androst-16-en-3β-ol (7148-51-8) + (3β,5α)-17-(((4'-trimethylsilyl)ethynyl)phenyl)androst-16-en-3-ol

Conditions	Yield
Stage #1: 17-bromo-3β-hydroxy-5α-androstan-16-ene With tert.-butyl lithium; XPhos In tetrahydrofuran; pentane at -78℃; for 0.5h; Schlenk technique; Inert atmosphere; Stage #2: (4-bromophenoxy)trimethylsilane With tris-(dibenzylideneacetone)dipalladium(0) In tetrahydrofuran; toluene; pentane at -78 - 20℃;

Epiandrosterone (481-29-8) → 5α-androst-16-en-3β-ol (7148-51-8) + (3β,5α)-17-(2’-methylphenyl)-androst-16-en-3-ol

Conditions	Yield
Multi-step reaction with 2 steps 1.1: hydrazine hydrate; triethylamine / ethanol / 16 h / 50 °C / Inert atmosphere 1.2: 1 h / 0 - 20 °C 2.1: XPhos; tert.-butyl lithium / pentane; tetrahydrofuran / 0.5 h / -78 °C / Schlenk technique; Inert atmosphere 2.2: -78 - 20 °C View Scheme
Multi-step reaction with 3 steps 1: hydrazine hydrate; triethylamine / ethanol / 16 h / 50 °C / Inert atmosphere 2: triethylamine; iodine / tetrahydrofuran / 20 °C / Inert atmosphere; Cooling with ice 3: sodium carbonate; tetrakis(triphenylphosphine) palladium(0) / benzene; methanol; water / 24 h / Schlenk technique; Reflux View Scheme

Epiandrosterone (481-29-8) → 5α-androst-16-en-3β-ol (7148-51-8) + (3β,5α)-17-(3’-methylphenyl)-androst-16-en-3-ol

Conditions	Yield
Multi-step reaction with 2 steps 1.1: hydrazine hydrate; triethylamine / ethanol / 16 h / 50 °C / Inert atmosphere 1.2: 1 h / 0 - 20 °C 2.1: XPhos; tert.-butyl lithium / pentane; tetrahydrofuran / 0.5 h / -78 °C / Schlenk technique; Inert atmosphere 2.2: -78 - 20 °C View Scheme

Epiandrosterone (481-29-8) → 5α-androst-16-en-3β-ol (7148-51-8) + (3β,5α)-17-(((4'-trimethylsilyl)ethynyl)phenyl)androst-16-en-3-ol

Conditions	Yield
Multi-step reaction with 2 steps 1.1: hydrazine hydrate; triethylamine / ethanol / 16 h / 50 °C / Inert atmosphere 1.2: 1 h / 0 - 20 °C 2.1: XPhos; tert.-butyl lithium / pentane; tetrahydrofuran / 0.5 h / -78 °C / Schlenk technique; Inert atmosphere 2.2: -78 - 20 °C View Scheme

2-Methylphenylboronic acid (16419-60-6) + 17-iodo-3β-hydroxy-5α-androstan-16-ene (95043-81-5) → 5α-androst-16-en-3β-ol (7148-51-8) + (3β,5α)-17-(2’-methylphenyl)-androst-16-en-3-ol

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In methanol; water; benzene for 24h; Suzuki Coupling; Schlenk technique; Reflux; Overall yield = 22 mg;	A n/a B 31 %Spectr.

3β-hydroxy-17-hydrozone-5α-androstane (10481-80-8) → 5α-androst-16-en-3β-ol (7148-51-8) + (3β,5α)-17-(2’-methylphenyl)-androst-16-en-3-ol

Conditions	Yield
Multi-step reaction with 2 steps 1: triethylamine; iodine / tetrahydrofuran / 20 °C / Inert atmosphere; Cooling with ice 2: sodium carbonate; tetrakis(triphenylphosphine) palladium(0) / benzene; methanol; water / 24 h / Schlenk technique; Reflux View Scheme

methanol (67-56-1) + carbon monoxide (201230-82-2) + 5α-androst-16-en-3β-ol (7148-51-8) → 3β-hydroxy-5α-androstane-16α-carboxylic acid methyl ester (143101-95-5)

Conditions	Yield
bis-triphenylphosphine-palladium(II) chloride at 100 - 120℃; under 120 Torr;	83%

ethanol (64-17-5) + carbon monoxide (201230-82-2) + 5α-androst-16-en-3β-ol (7148-51-8) → (3S,5S,8S,9S,10S,13R,14S,16R)-3-Hydroxy-10,13-dimethyl-hexadecahydro-cyclopenta[a]phenanthrene-16-carboxylic acid ethyl ester (143101-96-6)

Conditions	Yield
bis-triphenylphosphine-palladium(II) chloride at 120℃; under 120 Torr;	80%

5α-androst-16-en-3β-ol (7148-51-8) → 5α-androsta-2,16-diene (50588-44-8) + 3α-fluoro-5α-androst-16-ene

Conditions	Yield
With Nonafluorobutanesulfonyl fluoride; 1,8-diazabicyclo[5.4.0]undec-7-ene In toluene at 0 - 5℃; for 1h;	A 20% B 69%

5α-androst-16-en-3β-ol (7148-51-8) + C16H20Cl3NO10 → C26H40O7 + C26H40O7

Conditions	Yield
Stage #1: 5α-androst-16-en-3β-ol; C16H20Cl3NO10 With boron trifluoride diethyl etherate In dichloromethane at -15℃; for 16h; Molecular sieve; Stage #2: With water; sodium hydroxide In methanol for 1h; Overall yield = 67 %;	A 60% B n/a

5α-androst-16-en-3β-ol (7148-51-8) → 5α-androstan-3β-ol (1224-93-7, 7657-50-3, 7753-89-1, 10085-14-0, 15360-52-8, 15360-53-9, 36216-01-0, 36216-02-1, 1224-92-6)

Conditions	Yield
With acetic acid; platinum Hydrogenation;

5α-androst-16-en-3β-ol (7148-51-8) → 5α-androstanetriol-(3β.16α.17α) (14339-58-3)

Conditions	Yield
With pyridine; osmium(VIII) oxide; diethyl ether Schuetteln des Reaktionsprodukts mit wss. KOH und Mannit;

5α-androst-16-en-3β-ol (7148-51-8) + acetic anhydride (108-24-7) → 5α-androst-16-en-3β-yl acetate (72203-76-0)

Conditions	Yield
With pyridine

carbon monoxide (201230-82-2) + 5α-androst-16-en-3β-ol (7148-51-8) → (3S,5S,8S,9S,10S,13R,14S,16R)-3-Hydroxy-10,13-dimethyl-hexadecahydro-cyclopenta[a]phenanthrene-16-carbaldehyde (142794-26-1)

Conditions	Yield
With di-μ-chlorobis(norbornadiene)dirhodium(I); tributylphosphine; triethylamine In benzene at 120℃; under 90007.2 Torr;	72 % Spectr.

carbon monoxide (201230-82-2) + 5α-androst-16-en-3β-ol (7148-51-8) + isopropyl alcohol (67-63-0) → (3S,5S,8S,9S,10S,13R,14S,16R)-3-Hydroxy-10,13-dimethyl-hexadecahydro-cyclopenta[a]phenanthrene-16-carboxylic acid isopropyl ester (143101-97-7)

Conditions	Yield
bis-triphenylphosphine-palladium(II) chloride at 100℃; under 80 Torr;	69 % Chromat.

carbon monoxide (201230-82-2) + 5α-androst-16-en-3β-ol (7148-51-8) + isopropyl alcohol (67-63-0) → (3S,5S,8S,9S,10S,13R,14S,16R)-3-Hydroxy-10,13-dimethyl-hexadecahydro-cyclopenta[a]phenanthrene-16-carboxylic acid tert-butyl ester (143101-98-8)

Conditions	Yield
bis-triphenylphosphine-palladium(II) chloride at 100℃; under 80 Torr;	80 % Chromat.

5α-androst-16-en-3β-ol (7148-51-8) → 5alpha-Androstane-3beta,17alpha-diol (5856-11-1) + 3β,16α-dihydroxy-5α-androstane (22630-49-5)

Conditions	Yield
With sodium hydroxide; borane; dihydrogen peroxide 1.) THF, 4 h, 2.) overnight; Yield given; Multistep reaction;	A n/a B 1.58 g
With sodium hydroxide; borane; dihydrogen peroxide 1.) THF, 4 h, 2.) overnight; Yield given; Multistep reaction;	A 1.17 g B n/a

5α-androst-16-en-3β-ol (7148-51-8) → 16α,17α-epoxy-5α-androstane-3β-ol

Conditions	Yield
With 3-chloro-benzenecarboperoxoic acid In chloroform 1.) 0 deg C, 10 min, 2.) room temperature, 2 h;	1.1 g
With 3-chloro-benzenecarboperoxoic acid In chloroform

(2-hydroxyethyl)(methyl)amine (109-83-1) + carbon monoxide (201230-82-2) + 5α-androst-16-en-3β-ol (7148-51-8) → 5α-androstan-3β-ol (1224-93-7, 7657-50-3, 7753-89-1, 10085-14-0, 15360-52-8, 15360-53-9, 36216-01-0, 36216-02-1, 1224-92-6) + 3β-hydroxy-16α(β)-[N,N-(methyl, 2-hydroxyethylamino)methyl]-5α-androstane + (3S,5S,8S,9S,10S,13R,14S)-16-[1-[(2-Hydroxy-ethyl)-methyl-amino]-meth-(Z)-ylidene]-10,13-dimethyl-hexadecahydro-cyclopenta[a]phenanthren-3-ol

Conditions	Yield
With di-μ-chlorobis(norbornadiene)dirhodium(I); tributylphosphine; hydrogen In benzene at 120℃; under 60800 Torr; for 6h; Carbonylation; condensation; hydrogenation;	A 13.7 % Chromat. B 78.4 % Chromat. C 7.8 % Chromat.

2-aminobutanol (96-20-8, 13054-87-0) + carbon monoxide (201230-82-2) + 5α-androst-16-en-3β-ol (7148-51-8) → 5α-androstan-3β-ol (1224-93-7, 7657-50-3, 7753-89-1, 10085-14-0, 15360-52-8, 15360-53-9, 36216-01-0, 36216-02-1, 1224-92-6) + (3S,5S,8S,9S,10S,13R,14S)-16-[(1-Hydroxymethyl-propylamino)-methyl]-10,13-dimethyl-hexadecahydro-cyclopenta[a]phenanthren-3-ol

Conditions	Yield
With di-μ-chlorobis(norbornadiene)dirhodium(I); tributylphosphine; hydrogen In benzene at 120℃; under 60800 Torr; for 6h; Carbonylation; condensation; hydrogenation;	A 7.4 % Chromat. B 92.6 % Chromat.

N-(2-hydroxyethyl)-N-propylamine (16369-21-4) + carbon monoxide (201230-82-2) + 5α-androst-16-en-3β-ol (7148-51-8) → 5α-androstan-3β-ol (1224-93-7, 7657-50-3, 7753-89-1, 10085-14-0, 15360-52-8, 15360-53-9, 36216-01-0, 36216-02-1, 1224-92-6) + (3S,5S,8S,9S,10S,13R,14S)-16-[1-[(2-Hydroxy-ethyl)-propyl-amino]-meth-(Z)-ylidene]-10,13-dimethyl-hexadecahydro-cyclopenta[a]phenanthren-3-ol + (3S,5S,8S,9S,10S,13R,14S)-16-{[(2-Hydroxy-ethyl)-propyl-amino]-methyl}-10,13-dimethyl-hexadecahydro-cyclopenta[a]phenanthren-3-ol

Conditions	Yield
With di-μ-chlorobis(norbornadiene)dirhodium(I); tributylphosphine; hydrogen In benzene at 120℃; under 60800 Torr; for 6h; Carbonylation; condensation; hydrogenation;	A 6.5 % Chromat. B 4.4 % Chromat. C 89.0 % Chromat.

carbon monoxide (201230-82-2) + 5α-androst-16-en-3β-ol (7148-51-8) + propan-1-ol-3-amine (156-87-6) → 5α-androstan-3β-ol (1224-93-7, 7657-50-3, 7753-89-1, 10085-14-0, 15360-52-8, 15360-53-9, 36216-01-0, 36216-02-1, 1224-92-6) + 3β-hydroxy-16α(β)-[N-(3-hydroxypropylamino)methyl]-5α-androstane

Conditions	Yield
With di-μ-chlorobis(norbornadiene)dirhodium(I); tributylphosphine; hydrogen In benzene at 120℃; under 60800 Torr; for 6h; Carbonylation; condensation; hydrogenation;	A 8.2 % Chromat. B 91.8 % Chromat.

pyridine (110-86-1) + diethyl ether (60-29-7) + 5α-androst-16-en-3β-ol (7148-51-8) + OsO4 → 5α-androstanetriol-(3β.16α.17α) (14339-58-3)

Conditions	Yield
Schuetteln des Reaktionsprodukts mit wss. KOH und Mannit;

5α-androst-16-en-3β-ol (7148-51-8) → 3β,16β-dihydroxy-5α-androstane (7657-53-6)

Conditions	Yield
Multi-step reaction with 3 steps 1: 1.) borane, 2.) aq. NaOH, H2O2 / 1.) THF, 4 h, 2.) overnight 2: 1 g / CrO3 / acetone / 0.5 h / 0 deg C to room temperature 3: 0.85 g / NaBH4 / methanol / 0.67 h / 0 °C View Scheme

5α-androst-16-en-3β-ol (7148-51-8) → 11α,16β-dihydroxy-5α-androstane-3-one (24317-68-8)

Conditions	Yield
Multi-step reaction with 4 steps 1: 1.) borane, 2.) aq. NaOH, H2O2 / 1.) THF, 4 h, 2.) overnight 2: 1 g / CrO3 / acetone / 0.5 h / 0 deg C to room temperature 3: 0.85 g / NaBH4 / methanol / 0.67 h / 0 °C 4: 4.5 percent / Cephalosporium aphidicola in shake culture / ethanol / 168 h View Scheme

5α-androst-16-en-3β-ol (7148-51-8) → 5α-androstane-3,16-dione (1035-71-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: 1.) borane, 2.) aq. NaOH, H2O2 / 1.) THF, 4 h, 2.) overnight 2: 1 g / CrO3 / acetone / 0.5 h / 0 deg C to room temperature View Scheme

Upstream product

• 32138-70-8 17-Iodandrost-16-en-3β-ol 
• 94438-53-6 17-Brom-androst-16-en-3β-ol 
• 18339-16-7 5α-androst-16-en-3-one 
• 555-31-7 aluminum isopropoxide 
• 67-63-0 isopropyl alcohol 
• 72203-76-0 5α-androst-16-en-3β-yl acetate 
• 94438-53-6 17-bromo-3β-hydroxy-5α-androstan-16-ene 
• 95043-81-5 17-iodo-3β-hydroxy-5α-androstan-16-ene 
• 17320-46-6 17-chloro-3β-hydroxy-5α-androstan-16-ene 
• 939496-37-4 16R-bromopregnane-3S,20S-diol 
• 521-18-6 Stanolone 
• 19291-29-3 17β-methoxycarbonyloxy-5α-androstan-3-one 
• 1239-31-2 3β-acetoxy-5α-androstan-17-one 
• 86270-19-1 17-nitroimino-5α-androstan-3β-yl acetate 

Downstream Products

• 1224-93-7 5α-androstan-3β-ol 
• 7657-50-3 5α-androstan-3α-ol 
• 18339-16-7 5α-androst-16-en-3-one 
• 5856-11-1 5alpha-Androstane-3beta,17alpha-diol 
• 22630-49-5 3β,16α-dihydroxy-5α-androstane 

Relevant articles and documents

The fragmentation reaction of 16R-bromopregnane-3S,20S-diol

16R-Bromopregnane-3S,20S-diol reacted with potassium t-butoxide to afford androst-16-en-3S-ol in a moderate yield via fragmentation reaction. The latter is a key intermediate for the synthesis of 5α-androst-16-en-3-one, as boar sex pheromone, and other steroidal drugs. In addition, 16R,20S-epoxypregnane-3S-ol was also obtained as a major product by changing the reaction solvent.

Stille and Suzuki Cross-Coupling Reactions as Versatile Tools for Modifications at C-17 of Steroidal Skeletons – A Comprehensive Study

Herein, we report on a comparative Stille and Suzuki cross-coupling study of steroidal vinyl (pseudo)halides with different boronic acids and tributyltin organyls. Furthermore, we have investigated the “inverse” case of those cross-coupling reactions, i.e., the reaction of a steroidal vinylpinacolatoborane or a tributyltin steroid with various bromides. The development of both methods allows the introduction of different residues at C-17 of steroid skeletons providing access to a broad variety of steroid analogues which are of high interest for biological screenings or natural product synthesis. (Figure presented.).

5α-Androst-16-en-3α-ol β-D-glucuronide, precursor of 5α-androst-16-en-3α-ol in human sweat

5α-Androst-16-en-3α-ol (α-androstenol) is an important contributor to human axilla sweat odor. It is assumed that α-andostenol is excreted from the apocrine glands via a H2O-soluble conjugate, and this precursor was formally characterized in this study for the first time in human sweat. The possible H2O-soluble precursors, sulfate and glucuronide derivatives, were synthesized as analytical standards, i.e., α-androstenol, β-androstenol sulfates, 5α-androsta-5,16-dien- 3β-ol (β-androstadienol) sulfate, α-androstenol β-glucuronide, α-androstenol α-glucuronide, β-androstadienol β-glucuronide, and α-androstenol β-glucuronide furanose. The occurrence of α-androstenol β-glucuronide was established by ultra performance liquid chromatography (UPLC)/MS (heated electrospray ionization (HESI)) in negative-ion mode in pooled human sweat, containing eccrine and apocrine secretions and collected from 25 female and 24 male underarms. Its concentration was of 79 ng/ml in female secretions and 241 ng/ml in male secretions. The release of α-androstenol was observed after incubation of the sterile human sweat or α-androstenol β-glucuronide with a commercial glucuronidase enzyme, the urine-isolated bacteria Streptococcus agalactiae, and the skin bacteria Staphylococcus warneri DSM 20316, Staphylococcus haemolyticus DSM 20263, and Propionibacterium acnes ATCC 6919, reported to have β-glucuronidase activities. We demonstrated that if α- and β-androstenols and androstadienol sulfates were present in human sweat, their concentrations would be too low to be considered as potential precursors of malodors; therefore, the H2O-soluble precursor of α-androstenol in apocrine secretion should be a β-glucuronide. Copyright