A series of phosphite-oxazoline ligands was tested in the Rh-catalyzed hydrosilylation of ketones. Systematic variation of the electronic and steric properties at the biphenyl phosphite moiety and at the oxazoline moiety provide useful information about the ligand parameters that control the enantiodiscrimination. The results show that the enantiomeric excesses are dependent on the properties on both the phosphite and oxazoline moieties of the ligand and on steric and electronic properties of the substrate. Low-to-moderate enantiomeric excesses (up to 62%) were obtained in the hydrosilylation of several aryl ketones. (c) 2006 Elsevier B.V. All rights reserved.