Synthesis of some 16,17-secoandrost-5-ene derivatives

Abstract

Starting from 3β-acetoxy-17-oxo-16,17-secoandrost-5-ene-16-nitrile (1), 3β-acetoxy-16,17-secoandrost-5-ene-16-nitrile (4) was synthesized by a three-stage procedure. First, the formyl group of compound 1 was reduced, to yield the alcohol 2. Compound 2 was further transformed to the mesyloxy derivative 3, whose reduction with NaBH3CN gave compound 4. Apart from compound 4 as the main reaction product, two additional products were obtained, for which the GC/MS analysis suggested that they are 8(14) and 14 derivatives of compound 4. Compound 4 was transformed into 3β-hydroxy-16,17-sesoandrost-5-ene-16-nitrile (7), the Oppenauer oxidation of which afforded 3-oxo-16,17-secoandrost-4-ene-16-nitrile (8).

Keywords

• androst-5-ene derivatives
• 16, 17-seco steroids
• reduction of aldehydes