Configuration Sampling With Five-Membered Atropisomeric P,N-Ligands.

Here we report a strategy for the systematic variation of atropisomeric C1 -symmetric P,N ligands to incrementally change the position of the groups within the chiral pocket without modifying their steric parameters. More specifically, the effects of systematic modification of the nitrogen heterocycle in atropisomeric C1 -symmetric stack ligands have been investigated in this study. The versatility and applicability of this approach has been demonstrated in mechanistically distinct catalytic enantioselective transformations, resulting in the identification of a P,N-ligand for a highly enantioselective synthesis of organoboranes.