Synthesis of sesquiterpene polyene hydroperoxides by regio- and stereoselective transposition reactions

Article abstract of DOI:10.1016/S0040-4020(98)00782-0

Isomeric unsaturated alcohols (8), (16), (18) and (20), on exposure to hydrogen peroxide or water in the presence of an acid catalyst, undergo exceptionally regio- and stereoselective substitution reactions to form hydroperoxide (3) and alcohol (8) respectively. E/Z isomeric ratios of transposition products indicate that the intermediate acyclic carbocations (21) and (22) are not interconverting under the reaction conditions. Practical syntheses of α-farnesene autoxidation products have been developed based on these transposition reactions.