SYNTHESIS OF SESQUITERPENE POLYENE HYDROPEROXIDES BY REGIO-SELECTIVE AND STEREOSELECTIVE TRANSPOSITION REACTIONS

Isomeric unsaturated alcohols (8), (16), (18) and (20), on exposure to hydrogen peroxide or water in the presence of an acid catalyst, under go exceptionally regio- and stereoselective substitution reactions to form hydroperoxide (3) and alcohol (8) respectively. En isomeric ratio s of transposition products indicate that the intermediate acyclic car bocations (21) and (22) are not interconverting under the reaction con ditions. Practical syntheses of alpha-farnesene autoxidation products have been developed based on these transposition reactions. (C) 1998 E lsevier Science Ltd. All rights reserved.