The influence of structural modifications of the diamine ligand and the ZnR2 precursor in the [ZnR2–diamine]-catalyzed asymmetric hydrosilylation of prochiral ketones with PMHS in aprotic medium is reported. A new diamine ligand giving up to 91 % ee in the reduction of acetophenone is described. The scope of this reduction system has been investigated using variously functionalized ketones and some deactivation pathways have been identified.