Kinetic resolution using enantioimpure catalysts: Mechanistic considerations of complex rate laws

Kinetic resolutions in which the reactions exhibit complex rate laws are di scussed. When enantioimpure catalysts are employed, a conversion-dependent selectivity factor k(rel) may in some cases be observed due to "kinetic par titioning" of catalysts within a reaction network. Both asymmetric amplific ations and depletions may be observed, and the effects are separate from-an d may in some cases be superimposed on-the classic nonlinear effect due to catalyst interactions as those predicted by Kagan's MLn models. Considerati on of the conversion dependence of the selectivity factor using enantioimpu re catalysts reveals significant detail about the reaction mechanism for th e enantiopure case and may offer insights for practical application of kine tic resolution. Examples from the literature are analyzed in the context of kinetic partitioning.