An efficient synthesis of 5alpha-androst-1-ene-3,17-dione

Steroids. 2006 Dec;71(13-14):1088-90. doi: 10.1016/j.steroids.2006.09.008. Epub 2006 Nov 22.


5alpha-Androst-1-ene-3,17-dione (5) as a prodrug of 1-testosterone (4) was prepared in four steps from 17beta-Acetoxy-5alpha-androstan-3-one (stanolone acetate) (1) in high yield. Thus, stanolone acetate (1) was brominated in the presence of hydrogen chloride in acetic acid to give 17beta-acetoxy-2-bromo-5alpha-androstan-3-one (2), which underwent dehydrobromination using lithium carbonate as base with lithium bromide as an additive to give 17beta-acetoxy-5alpha-androst-1-en-3-one (3) in almost quantitative yield with 97% of purity. Compound (3) was hydrolyzed with sodium hydroxide to give 17beta-hydroxy-5alpha-androst-1-en-3-one (4,1-testosterone), which was oxidized with chromium trioxide to afford 5alpha-androst-1-ene-3,17-dione (5). The overall yield of 5 was 78.2% with purity of 99%. In this method, the formation of 4-ene was diminished when 1-ene was introduced, and its mechanism was also discussed.

MeSH terms

  • Androstenedione / chemical synthesis*
  • Androstenedione / chemistry
  • Chromatography, High Pressure Liquid
  • Magnetic Resonance Spectroscopy
  • Mass Spectrometry
  • Spectrophotometry, Ultraviolet


  • Androstenedione
  • 5-androstene-3,17-dione