Synthesis of the allylic gonadal steroids, 3 α-hydroxy-4-pregnen-20-one and 3 α-hydroxy-4-androsten-17-one, and of 3 α-hydroxy-5 α-pregnan-20-one

• Published in: Steroids Vol. 45; no. 1; pp. 39 - 51
• Main Authors: Wiebe, J.P., Deline, C., Buckingham, K.D., Dave, Vinod, Stothers, J.B.
• Format: Journal Article
• Language: English
• Published: NEW YORK Elsevier Inc 1985; Elsevier; Elsevier Science
• Subjects: Alicyclic compounds, terpenoids, prostaglandins, steroids; Androstenedione; Androsterone - analogs & derivatives; Androsterone - chemical synthesis; Biochemistry & Molecular Biology; Chemistry; Endocrinology & Metabolism; Exact sciences and technology; Gas Chromatography-Mass Spectrometry; Life Sciences & Biomedicine; Magnetic Resonance Spectroscopy; Organic chemistry; Oxidation-Reduction; Pregnanes - chemical synthesis; Pregnanolone - chemical synthesis; Preparations and properties; Progesterone; Science & Technology; Steroids; Chemical reduction; Steroid; Diol; Epimerization; Diketone; Progesterone; Sex steroid hormone; Enone
• ISSN: 0039-128X; 1878-5867
• DOI: 10.1016/0039-128X(85)90064-9

A method for the convenient synthesis of the recently isolated allylic gonadal steroids, 3 α-hydroxy-4-pregnen-20-one (3 α-dihydroprogesterone; 3 α-DHP) and 3 α-hydroxy-4-androsten-17-one (3 α-HA), was developed using 4-pregnene-3,20-dione (progesterone) and 4-androstene-3,17-dione as substrates and potassium trisiamylborohydride (KS-Selectride) as reducing agent. Similar reactions were also used for the reduction of 5 α-pregnane-3,20-dione to 3 α-hydroxy-5 α-pregnan-20-one (3 α-HP). The yields were about 15%, 50%, and >90% for 3 α-DHP, 3 α-HA and 3 α-HP, respectively. Structures of the products, including the 3 β-isomers and the 17 α-epimer, formed in these reactions were determined by NMR and mass spectroscopic methods.