THE CHEMISTRY OF 9α-HYDROXYSTEROIDS. 1. PREPARATION OF 9α,17β-DIHYDROXY-17α-ETHYNYLANDROST-4-EN-3-ONE

Article abstract of DOI:10.1016/0039-128X(88)90002-5

9α-Hydroxyandrost-4-ene-3,17-dione 1, when allowed to react with dipotassium acetylide in tetrahydrofuran, resulted, after chromatographic separation, in 4-methyl-19-norandrosta-4,9-diene-1,17-dione 2, 4ξ-methyl-19-norandrosta-5(10),9(11)-diene-1,17-dione 3, 4-methyl-17α-ethynyl-17β-hydroxy-19-norandrosta-4,9-dien-1-one 4, 4ξ-methyl-17α-ethynyl-17β-hydroxy-19-norandrosta-5(10),9(11)-dien-1-one 5, and 17α-ethynyl-17β-hydroxy-9,10-secoandrost-4-ene-3,9-dione 6.Selective protection of Δ⁴-3-ketone of 9α-hydroxyandrost-4-ene-3,17-dione 1 as its dienol methyl ether 7, and subsequent reaction with lithium acetylide-ethylenediamine followed by acidic hydrolysis, afforded 9α,17β-dihydroxy-17α-ethynylandrost-4-en-3-one 8.