SYNTHESIS AND ABSOLUTE-CONFIGURATION OF NEW CHIRAL EPOXYALCOHOLS BY STEREOSELECTIVE EPOXIDATION OF ALLYLIC AND HOMOALLYLIC ALCOHOLS WITH A (1R)-(-CAMPHOR SKELETON())

The chiral nonracemic alcohols 1-5 were stereoselectively epoxidized w ith the VO(acac)(2)/t-butyl hydroperoxide system. The epoxyalcohols 6- 9 resulting from alcohols 1-4 were synthesized in high yields and the obtained diastereoisomers were isolated in pure form by chromatography . The homoallylic alcohol 5 epoxidized 100% diastereoselectively to 10 . The epoxyalcohol 10 underwent a stereoselective intramolecular cycli sation during the epoxydation with rearrangement of the camphor skelet on to the oxatricyclo derivative 11. The absolute configurations of th e new chiral compounds were determined by NMR methods. Copyright (C) 1 996 Elsevier Science Ltd