The enantiomers of a bis[5]helicenediol ligand ([5]HELOL) have been synthesized in appreciableamounts by a procedure in which key steps are the union of p-benzoquinone with an enol ether of3-acetylphenanthrene and the displacement of phenol and phenol ether functions by alcohols (theRussig−Laatsch reaction). This diol catalyzes the addition of diethylzinc to aldehydes and givesnonracemic alcohols with enantiomeric excesses as high as 81%. The stereoselectivities and yieldsare much greater than when the catalyzing diol is BINOL. The enantioselectivities are greateralso than those of other reactions catalyzed by helicene ligands.