Abstract Both (R)-and (S)-5, 7-O-dimethyleucomol 1b (R= Me) were synthesized in 57% overall yield in> 96% enantiomeric excess. The key step involves the enantioselective α hydroxylation of the lithium enolate of 8 by readily available (+)-and (−)-[(8, 8- dimethoxycamphoryl) sulfonyl] oxaziridine 9c.