An efficient protocol for the synthesis of chiral polyhydroxy-(E, E)-1-chlorodienols and (E)-5- hydroxy enynes from chiral 4, 5-epoxy trans allyl chlorides and 4, 5-O-isopropylidene allyl chlorides is described by using stoichiometric amount of LiNH2 or LDA in HMPA: THF (1: 5) useful in the synthesis of biologically active natural products.