3-beta-Acetoxyandrost-5-en-17-one (I) was converted into enol triflate (II) by reaction with trifluoromethanesulfonic anhydride in the presence of a hindered base. The subsequent palladium-catalyzed coupling of (II) with ethyl vinyl ether produced a mixture of regioisomeric enol ethers which, after acid hydrolysis, afforded aldehyde (III) and ketone (IV). The minor aldehyde compound (III) was isolated by liquid chromatography and then converted into oxime (V) using hydroxylamine hydrochloride and NaOAc. Finally, the acetate ester group of (V) was hydrolyzed by means of methanolic KOH.