Studies towards the synthesis of polyoxygenated steroids. Reaction of some tri- and tetra-substituted monoene steroids with RuO4☆

Abstract The course of the reaction of ruthenium tetroxide with some tri- and tetra-substituted nuclear monoene steroids, namely δ 4 , δ 5 , δ 7 and δ 8(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 RuO 4 oxidations, we found that trisubstituted double bonds gave α-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 δ 8(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.

[1]  K. Sharpless,et al.  Asymmetric epoxidation provides shortest routes to four chiral epoxy alcohols which are key intermediates in syntheses of methymycin, erythromycin, leukotriene C-1, and disparlure , 1981 .

[2]  Donald G. Lee.  Phase Transfer Assisted Permanganate Oxidations , 1982 .

[3]  V. Martín,et al.  A greatly improved procedure for ruthenium tetroxide catalyzed oxidations of organic compounds , 2002 .

[4]  Kurt Wüthrich,et al.  Experimental techniques of two-dimensional correlated spectroscopy , 1980 .

[5]  Y. Yanuka,et al.  Notes- Preparation and Degradation of 3α-Hydroxycholanic Acid , 1959 .

[6]  M. Sprecher,et al.  The synthesis of 10-hydroxy-10α-testosterone , 1964 .

[7]  G. Ourisson,et al.  Cholesterol and Companions. IV. Oxidation of ▵7-Stenols with Selenium Dioxide , 1953 .

[8]  Donald G. Lee,et al.  The oxidation of methyl cinnamate by ruthenium tetroxide , 1976 .

[9]  L. Fieser,et al.  Selective Oxidation with N-Bromosuccinimide. II. Cholestane-3β,5α,6β-triol , 1949 .

[10]  P. Rylander,et al.  Use of Ruthenium Tetroxide as a Multi-purpose Oxidant , 1958 .

[11]  A. Bax,et al.  Correlation of proton chemical shifts by two-dimensional Fourier transform NMR , 1981 .

[12]  C. Djerassi,et al.  Oxidations with Ruthenium Tetroxide , 1953 .

[13]  R. Beyler,et al.  Approaches to the Total Synthesis of Adrenal Steroids.1 V. 4b-Methyl-7- ethylenedioxy-1,2,3,4,4aα,4b,5,6,7,8,10,10a β-dodecahydrophenanthrene-4 β-ol-1-one and Related Tricyclic Derivatives , 1953 .

[14]  H. Nakata.  Oxidation reaction of steroid alcohols by ruthenium tetroxide. , 1963, Tetrahedron.

[15]  E. Caspi,et al.  Oxidation of steroidal ketones. VII. Cleavage of steroidal conjugated ketones with ruthenium tetroxide , 1969 .

[16]  Y. Mazur,et al.  Mass spectrometry as a diagnostic tool for 5-hydroxysteroids☆ , 1973 .

[17]  A. D. Kagarlitskii,et al.  The oxidation of organic compounds , 1970 .

[18]  Vincenzo Piccialli,et al.  Four new trihydroxylated sterols from the sponge Spongionella gracilis , 1987 .