Collect. Czech. Chem. Commun. 1987, 52, 2991-3012

Solvolytic rearrangements in 4β,5-cyclopropano-5β-cholestane-3β,19-diol 3-acetate 19-p-toluenesulphonate

Jiří Joskaa, Jan Fajkoša and František Turečekb

a Institute of Organic Chemistry and Biochemistry, Czechoslovak Academy of Sciences, 166 10 Prague 6
b The J. Heyrovský Institute of Physical Chemistry and Electrochemistry, Czechoslovak Academy of Sciences, 121 38 Prague 2


Acetolysis of the tosylate VIII proceeded under participation of the cyclopropane ring at the electron-deficient center formed during the reaction to yield three products all having modified steroid skeletons. They were the diene XXIII, the unsaturated acetate XI, and the saturated 4β,10β-cycloderivative XIII carrying two acetoxy groups in the molecule. For the purpose of spectral studies and structure elucidation the acetolysis has been carried out with the labelled tosylate XXXII the synthesis of which is described and analogous three labelled products were isolated. The structures of these products were established on the basis of spectral and chemical evidence and a mechanism of the rearrangements is proposed.