
%0 Journal Article
%A Bathurst, ETJ 
%A Coxon, JM 
%A Hartshorn, MP 
%T Reactions of 5-Hydroxy steroids. XIII. The acid-catalysed reactions of Cholestane-4,5-diol 4-acetates and Cholestane-4,5-diol diacetates
%J Australian Journal of Chemistry
%D 1974/07/01
%V 27
%N 7
%P 1505-1513
%K 
%R https://doi.org/10.1071/CH9741505
%U https://www.publish.csiro.au/paper/CH9741505 
%X The reaction of 5&#945;-cholestane-4&#945;,5-diol 4-acetate (lb) with sulphuric acid-acetic anhydride-acetic acid occurs almost exclusively by loss of the 6&#945;-proton to give cholest-5-en-4a-yl acetate (3) while dehydration with thionyl chloride-pyridine occurs predominantly (c. 80%) by loss of the 6&#946;-proton. On reaction with D2SO4-DOAc-Ac2O, 5&#945;-cholestane-4&#946;,5-diol 4-acetate (7) undergoes backbone rearrangement to give olefins (9),(10) and (11) without incorporation of deuterium and thus excludes the intermediacy of olefins and cyclopropanes in the rearrangement process. The effect of substituents on these reactions has been rationalized by consideration of the initial conformation of the C5 carbonium ion. 
