The efficient asymmetric hydrosilylation of ketones with a chiral titanocene catalyst has been realized. In this procedure, (R,R)-ethylenebis(tetrahydroindenyl) titanium difluoride (1) was used as the precatalyst, and alcohol additives were employed. Aromatic and alpha,beta-unsaturated ketones were reduced to the corresponding alcohols with a high level of enantioselectivity.
“Titanocene-catalyzed asymmetric ketone hydrosilylation: The effect of catalyst activation protocol and additives on the reaction rate and enantioselectivity”, J. Am. Chem. Soc., 1999, 121(24), 5640-5644.