Epoxidation and reduction of DHEA, 1,4,6-androstatrien-3-one and 4,6-androstadien-3beta,17beta-diol.
Dehydroepiandrosterone (DHEA) reacted with m-chloroperoxybenzoic acid(m-CPBA) to form 3beta-hydroxy-5alpha,6alpha-epoxyandrostan-17-one (1), but it did not react with 30% H2O2. 1,4,6-Androstatrien-3,17-dione (2) was obtained from DHEA and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone in dioxane. Compound 2 was reacted with 30%H2O2 and 5% NaOH in methanol to give 1alpha,2alpha-epoxy-4,6-androstadien-3,17-dione (3),which was stereoselectively reduced with NaBH4 to form 1alpha,2alpha-epoxy-4,6-androstadien-3beta,17beta-diol (7) and reacted with Li metal in absolute ethanol-tetrahydrofuran mixture to give 2-ethoxy-1,4,6-androstatrien-3,17-dione (8). Compound 2 was also epoxidized with m-CPBA in dichloromethane to afford 6alpha,7alpha-epoxy-1,4-androstadien-3,17-dione (4),which was reacted with NaBH4 to synthesize 6alpha,7alpha-epoxy-4-androsten-3beta,17beta-diol (9). Compound 4 was reduced with Li metal in absolute ethanol-tetrahydrofuran mixture to form 7beta-ethoxy-6alpha-hydroxy-1,4-androstadien-3,17-dione (10). Compound 2 was reduced with NaBH4 in absolute ethanol to form 4,6-androstadien-3beta,17beta-diol (5), which was reacted with 30% H2O2 to give the original compound, but which reacted with m-CPBAto give 4beta,5beta-epoxy-6-androsten-3beta,17beta-diol (6).
Ma
Eunsook
E
College of Pharmacy, Catholic University of Daegu, Hayang, 712-702, Korea. masook@cu.ac.kr
Kim
Eunjeong
E
D000731:Androstanes / Q000138:chemical synthesis* / Q000737:chemistry*; D000736:Androstenes / Q000138:chemical synthesis* / Q000737:chemistry*; D001894:Borohydrides; D003687:Dehydroepiandrosterone / Q000737:chemistry*; D004852:Epoxy Compounds / Q000138:chemical synthesis*; D007202:Indicators and Reagents; D007700:Kinetics; D008958:Models, Molecular; D008968:Molecular Conformation; D010084:Oxidation-Reduction
D000731:Androstanes; D000736:Androstenes; D001894:Borohydrides; D004852:Epoxy Compounds; D007202:Indicators and Reagents; D003687:Dehydroepiandrosterone; C025364:sodium borohydride