SYNTHESIS OF POLYOXYGENATED STEROIDS .2. STUDIES TOWARDS THE SYNTHESIS OF POLYOXYGENATED STEROIDS - REACTION OF SOME TRI-SUBSTITUTED AND TETRA-SUBSTITUTED MONOENE STEROIDS WITH RUO4

The course of the reaction of ruthenium tetroxide with some tri- and tetra-substituted nuclear monoene steroids, namely DELTA4, DELTA5, DELTA7 and DELTA8(14)-steroids, has been investigated in acetone-water or carbon tetrachloride as solvent systems using stoichiometric amounts of the oxidant. In contrast with results previously reported for RuO4 oxidations, we found that trisubstituted double bonds gave alpha-hydroxy ketones and/or 1,2-diols rather than the expected products deriving from the scission of the carbon-carbon double bond. Scission of the double bond indeed occurs when fully substituted steroidal alkenes are oxidized. only in the case of the DELTA8(14)-steroid, an allylic oxidation product wa obtained in addition to the scission product. The change in the solvent system seems to profoundly affect the course of the reaction.