Collect. Czech. Chem. Commun. 1989, 54, 751-759

Solvolytic rearrangements in 4β,5-cyclopropano-5β-androstane-3β,17β,19-triol 3-acetate 17-benzoate 19-p-toluenesulfonate

Jan Fajkoš and Jiří Joska

Institute of Organic Chemistry and Biochemistry, Czechoslovak Academy of Sciences, 166 10 Prague 6


The title tosylate V was prepared from the tosylate III by Simmons-Smith methylenation. Its acetolysis afforded three products with modified steroid skeletons: The diene VIII, the olefin XI, and the pentacyclic diacetate XIII. The 3-oxo derivatives XIV, XVI, XVII, and XIX-compounds of potentional biological interest-were prepared as follows: Oxidation of the monoacetate X followed by hydrolysis yielded the testosterone analogue XIV and oxidation of the diol IX gave the dione XVI. Using similar reaction sequence the triol diester XII afforded the oxo compounds XVII and XIX.