Epoxidation and Reduction of DHEA, 1,4,6-Androstatrien-3-one and 4,6-Androstadien-3β,17β-diol

Dehydroepiandrosterone (DHEA) reacted with m-chloroperoxybenzoic acid (m-CPBA) to form 3β-hydroxy-5α,6α-epoxyandrostan-17-one (1), but it did not react with 30% H(2)O(2). 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% H(2)O(2) and 5% NaOH in methanol to give 1α,2α-epoxy-4,6-androstadien-3,17-dione (3), which was stereoselectively reduced with NaBH(4) to form 1α,2α-epoxy-4,6-androstadien-3β,17β-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 6α,7α-epoxy-1,4-androstadien-3,17-dione (4), which was reacted with NaBH(4) to synthesize 6α,7α-epoxy-4-androsten-3β,17β-diol (9). Compound 4 was reduced with Li metal in absolute ethanol-tetrahydrofuran mixture to form 7β-ethoxy-6α-hydroxy-1,4-androstadien-3,17-dione (10). Compound 2 was reduced with NaBH(4) in absolute ethanol to form 4,6-androstadien-3β,17β-diol (5), which was reacted with 30% H(2)O(2) to give the original compound, but which reacted with m-CPBA to give 4β,5β-epoxy-6-androsten-3β,17β-diol (6).