Asymmetric Catalysis Using Self-Assembled Chiral Bidentate P,P-Ligands

A strategy is described for modular catalyst development based upon metal-directed self-assembly of bifunctional subunits around a structural metal to form a heteroleptic complex in which a second set of ligating groups are now suitably disposed to bind a second metal to form a catalytic site. A library of chiral diphosphites was prepared via metal-directed self-assembly and used in a simple asymmetric allylic amination, giving enantiomeric excesses as high as 97%.