Kinetic Aspects of Nonlinear Effects in Asymmetric Catalysis

Probing catalyst systems for a nonlinear relationship between product enantioselectivity and catalyst enantiopurity is now commonly being used as a mechanistic tool. We show that in some cases striking consequences for reaction rate can ensue for reactions carried out using non-enantiopure catalysts. We also demonstrate how consideration of the kinetic behavior may serve to enhance the use of nonlinear effects as a diagnostic tool for identifying active catalytic species and for providing mechanistic insight. Kinetic information may also help in the development of efficient synthetic strategies using non-enantiopure systems.