Bicyclic Bridgehead Phosphoramidite-Based Hybrid Diphosphorus Ligands: Design, Synthesis, and Application in Catalytic Asymmetric Hydrogenation

A strategy for chiral ligand design has been developed that allows for incorporation of an achiral bicyclic bridgehead phosphoramidite to generate a class of hybrid diphosphorus ligands for high activity and asymmetric control. Using this concept, a series of chiral phosphine–phosphoramidite ligands bearing the sole chirality at the ligand backbone have been prepared and successfully employed in the Rh-catalyzed asymmetric hydrogenation of 2-vinylanilides for the synthesis of optically active anilines bearing an ortho-tertiary benzylic stereocenter.