Molecular Design, Synthesis, and Asymmetric Catalysis of a Hexacoordinated Chiral Phosphate Ion

We describe the design, synthesis, and characterization of a chiral hexacoordinated phosphate ion that features an octahedral P­(V) core consisting of two N,N,O-tridentate backbones. We further demonstrate that the corresponding hydrogen phosphate acts as an effective catalyst for a highly enantioselective Pictet–Spengler-type reaction, wherein the relationship between the structure of the chiral phosphate ion and its ability to dictate the absolute stereochemistry is revealed in conjunction with precise structural elucidation of the phosphate ion.