An Unexpected Directing Effect in the Asymmetric Transfer Hydrogenation of α,α-Disubstituted Ketones

α,α-Disubstituted ketones containing an aromatic ring or alkene are reduced in high enantiomeric excess using an asymmetric transfer hydrogenation catalyst. The sense of reduction indicates that the unsaturated region of the ketone adopts a position adjacent to the Ru-bound η6-arene ring in the reduction transition state.