The development of bidentate P,N ligands for asymmetric catalysis

In this review, an attempt is made to systemise the role which bidentate phosphinamine (PN) li-gands play in asymmetric catalysis. The ligands will be classified, not by the reaction to which their metal complexes have been applied, but by the nature of their donor atoms. In this manner the development of ligand architectural design can be more easily monitored. The asymmetric transformations to which metal complexes of these ligands have been applied include among others, palladium-catalysed allylic substitutions, copper-catalysed 1,4-additions to enones and rhodium-catalysed hydroboration of vinylarenes. Excellent enantioselectivities, regioselectivities and reactivities have been achieved in each of these processes.