P-Stereogenic N-Phosphine-Phosphite Ligands for the Rh-Catalyzed Hydrogenation of Olefins.

We have identified a successful family of simple P-stereogenic N-phosphine-phosphite ligands for the Rh-catalyzed asymmetric hydrogenation of olefins. These catalysts show excellent enantiocontrol for α-dehydroamino acid derivatives and α-enamides (ee's up to >99%) and promising results for the more challenging β-analogues (ee's up to 80%). The usefulness of these catalytic systems was further demonstrated with the synthesis of several valuable precursors for pharmacologically active compounds, with ee's at least as high as the best ones reported previously (up to >99%).