Oxidation reaction of steroid alcohols by ruthenium tetroxide

doi:10.1016/0040-4020(63)85009-7

Tetrahedron

Volume 19, Issue 12, 1963, Pages 1959-1963

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Abstract

Oxidation of steroid alcohols by ruthenium tetroxide gives corresponding ketones in almost quantitative yields. The reaction provides a simple and convenient procedure for converting secondary alcohols to ketones in neutral media. The reconversion of ruthenium dioxide, produced during the oxidation, into the tetroxide with an appropriate oxygen donor such as sodium metaperiodate makes possible the oxidation of a given steroid alcohol to a ketone in the presence of a catalytic amount of ruthenium tetroxide.

References (14)

S. Hara et al.
Chem. & Ind.
(1962)
L.M. Berkowitz et al.
J. Amer. Chem. Soc.
(1958)
J. Weinstock and M.E. Wolff, U.S. Patent 2,960,503, November 15,...
C. Djerassi et al.
J. Amer. Chem. Soc.
(1953)
F.S. Martin
J. Chem. Soc.
(1952)
F.S. Martin
J. Chem. Soc.
(1952)
F.G. Oberender et al.
J. Org. Chem.
(1959)
V. Burckhardt et al.
Helv. Chim. Acta
(1942)

There are more references available in the full text version of this article.

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Oxidation reaction of steroid alcohols by ruthenium tetroxide

Abstract

Chem. & Ind.

J. Amer. Chem. Soc.

J. Amer. Chem. Soc.

J. Chem. Soc.

J. Chem. Soc.

J. Org. Chem.

Helv. Chim. Acta