New chiral rhenium complexes of allylic, homoallylic and propargylic alcohols have been prepared and their reactivity versus various reagents has been studied. Starting from the allyl alcohol complex, a multistep sequence involving a chemoselective oxidation, a Wittig reaction and a reduction led without bond-shift to conjugated dienone and dienol. The complexed allyl acetate, prepared by reaction of acetic anhydride on the complexed allyl alcohol reacted with sodium dimethylmalonate in a diastereoselective fashion.