
TY  - JOUR
A1  - Bathurst, ETJ 
A1  - Coxon, JM 
A1  - Hartshorn, MP 
T1  - Reactions of 5-Hydroxy steroids. XIII. The acid-catalysed reactions of Cholestane-4,5-diol 4-acetates and Cholestane-4,5-diol diacetates
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1974
VL  - 27
IS  - 7
SP  - 1505
EP  - 1513
KW  - 
UR  - https://doi.org/10.1071/CH9741505 
N2  - 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. 
ER  -

