Stereochemically well-defined ruthenium(II) catalysts have been applied to the asymmetric transfer hydrogenation of a series of ketones. In one case, statistical experimental design was employed to optimize the enantiomeric excess of the product. In the case of the TsDPEN-based systems, the replacement of trans-1,2-diphenyl substitution with cis-, or deletion of one of the phenyl groups, results in significant deterioration of the enantiomeric excess. A new method is described for the synthesis of tethered amino alcohol-containing catalysts.