128229-19-6Relevant articles and documents
Allylic Hydroperoxides Formed by Singlet Oxygenation of Cholest-5-en-3-one
Dang, Hai-Shan,Davies, Alwyn G.,Schiesser, Carl H.
, p. 789 - 794 (2007/10/02)
Cholest-5-en-3-one (I) reacts with singlet oxygen to give the hemiperketal (II) (ca. 55percent), the epimeric 6β- and 6α-hydroperoxides (III) and (IV) (ca. 30 and 8percent respectively), and the dione (V) (ca 7percent).The hemiperketal (II) does not undergo an allylic rearrangement in solution, but the hydroperoxides (III) and (IV) epimerise by a radical chain mechanism. .Stereochemical problems connected with this system have been probed by carrying out parallel experiments and molecular mechanics calculations on the corresponding derivatives of methyloctahydronaphthalenone as model compounds.
