Supported Chiral Monodentate Ligands in Rhodium‐Catalysed Asymmetric Hydrogenation and Palladium‐Catalysed Asymmetric Allylic Alkylation

A family of monodentate polystyrene‐supported phosphites, phosphoramidites and phosphanes has been prepared and evaluated as ligands in rhodium‐catalysed asymmetric hydrogenation and palladium‐catalysed asymmetric allylic alkylation. The supported ligands yielded active and enantioselective catalysts, which in selected cases match the performance of the nonsupported counterparts. As expected, the performance of the supported ligands in the rhodium‐catalysed hydrogenation depends on the nature of the ligand, the type of polymeric support, as well as on the substrate. Additionally, the supported ligands have been applied in the monodentate ligand combination approach, by combining them with nonsupported monodentate ligands. The partially supported heteroligand combinations possess different catalytic properties than the related nonsupported combinations. The heteroligand species, however, are not formed selectively, and nonsupported homoleptic complexes also contribute to the overall activity. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)