Amine Additives Greatly Expand the Scope of Asymmetric Hydrosilylation of Imines

Slow addition of a primary amine to the reaction mixture greatly increases the scope of the titanium-catalyzed asymmetric reduction of imines 1 . An important added feature of this method is that chiral secondary amines 2 can be obtained in much higher optical purity (up to 99 % ee) than would be predicted from the E:Z ratios of the starting imines 1 .