The nucleophilic addition of alcohols, thiols, allylsilane, or triphenylphosphine on an allylic alcohol complexed to a chiral rhenium salt leads, in the presence of an acid, to the corresponding ethers, thioethers, 1,5-diene, and phosphonium salt in high yields. The high regioselectivity of these reactions is unambiguously established using a deuterated ligand.