In biological system, minor structural change of functional proteins and enzymes by noncovalent interaction or covalent modification can result in a distinct three-dimensional architecture, thus leading to modulation of the timely intra- or extracellular events to proceed with precise synergy.12 Inspired by this intriguing biological process, we hypothesized that exploration of con-formationally flexible chiral ligands would allow to dictate the diastereodivergency in asymmetric catalysis even when using a single metal.

We conceived a concept of biologically inspired design of chiral P,S-type ligands for the diastereodivergent asymmetric catalysis. This ligand architecture would exhibit a number of features:  (1) the coordination of P and S atoms with metal might provide highly enantioselective chiral environment, and (2) in analogy to the functional proteins and enzymes, modification of the N substitution would result in a distinct conformation of the catalyst.