Synthesis and reactions of some optically active epoxides formally derivedfrom tertiary allylic alcohols

The epoxyketones 2, 3 and 7-9 reacted with Grignard reagents in a highly st ereocontrolled manner to give the epoxyalcohols 20, 4-6 and 11-13 in high y ields. The epoxyalcohol 12 underwent a Payne rearrangement on base treatmen t to give the isomer 15 while epoxyalcohols 4, 5, 12 and 20 suffered ring-o pening (with retention of configuration) using tin(IV) chloride to afford c hlorodiols 18, 17, 19 and 21 respectively. On the other hand, the alcohols 4, 5 and 12 reacted with trialkylsilyl chlorides to furnish the chlorodiols 22, 24 and 23 respectively with inversion of configuration.