Reacción #2185444

ord-f99ff3009a834090b731b7ec52f1479a

Ecuación de reacción

CC(C)(C)C(=O)O[C@H]1CC[C@]2(C)[C@H]3CC[C@]4(C)C(=O)[C@H]5C[C@H]5[C@H]4[C@@H]3C=C[C@]2(O)C1
5β-hydroxy-15β,16β-methylene-3β-pivaloyloxyandrost-6-en-17-one
[K+].[OH-]
potassium hydroxide
→
C[C@]12CC[C@H]3[C@@H](C=C[C@]4(O)C[C@@H](O)CC[C@]34C)[C@@H]1[C@@H]1C[C@@H]1C2=O
3β,5β-dihydroxy-15β,16β-methyleneandrost-6-en-17-one

Reactantes

CC(C)(C)C(=O)O[C@H]1CC[C@]2(C)[C@H]3CC[C@]4(C)C(=O)[C@H]5C[C@H]5[C@H]4[C@@H]3C=C[C@]2(O)C1
5β-hydroxy-15β,16β-methylene-3β-pivaloyloxyandrost-6-en-17-one
—
7α-chloro
[K+].[OH-]
potassium hydroxide

Reactivos

[Zn]
zinc

Disolventes

CC(=O)O
acetic acid
C1CCOC1
tetrahydrofuran

Condiciones de reacción

Condiciones detalladas
See reaction.notes.procedure_details.

Procedimiento

The starting material of the process is 3β-hydroxy-15β,16β-methyleneandrost-5-en-17-one. The hydroxy in 7β position is introduced in a fermentation process using Botryodiplodia malorum, the resultant compound is acetylated in a regioselective manner with pivalic anhydride in the presence of 4-dimethylaminopyridine yielding the corresponding 3β-pivaloyloxy derivative. Said pivaloyloxy derivative was reacted with tert-butyl hydroperoxide in the presence of VO (acetonylacetonate)2 catalyst to give the 5β,6β-epoxy derivative which, in turn, was reacted with triphenylphosphine and carbon tetrachloride in dichloromethane to yield the 7α-chloro derivative. Said 7α-chloro derivative was reacted with zinc in a mixture of acetic acid and tetrahydrofuran yielding the 5β-hydroxy-15β,16β-methylene-3β-pivaloyloxyandrost-6-en-17-one which then was hydrolyzed with potassium hydroxide to give 3β,5β-dihydroxy-15β,16β-methyleneandrost-6-en-17-one.

Fuente

DOI: 10.6084/m9.figshare.5104873.v1Patente: US08450476B2uspto-grants-2013_05