Enantiodivergent Non-Linear Effects in Asymmetric Catalysis

In this paper, we theoretically discuss the enantiodivergent product formation in asymmetric catalysis, a process in which the sign of the overall product enantiomer switches upon a change of catalyst concentration. The presented model is based on a catalytic system that consists of both discrete and dimeric aggregated metal complexes, in competition and in equilibrium. These concepts were then expanded to a non-enantiopure catalyst, giving rise to enantiodivergent non-linear effects – a special case of a hyperpositive non-linear effects where the product enantiomer’s sign switches upon a change of the catalyst enantiomeric excess. Different cases are considered allowing a discussion of the influence of the parameters governing both models. Finally, we present experimental results that support the enantiodivergence while varying the concentration of enantiopure catalyst or while varying the enantiomeric excess of the catalyst, using chiral N-methylephedrine as a ligand for the enantioselective addition of dimethylzinc to benzaldehyde.