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.
Blackmond
D G
DG
Department of Chemistry, University of Hull, Hull HU6 7RX, United Kingdom. D.G.Blackmond@chem.hull.ac.uk
D000447:Aldehydes / Q000737:chemistry*; D002384:Catalysis; D019281:Dimerization; D007659:Ketones / Q000737:chemistry; D007700:Kinetics; D008956:Models, Chemical; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry; D013237:Stereoisomerism; D015032:Zinc / Q000737:chemistry*
D000447:Aldehydes; D007659:Ketones; D009942:Organometallic Compounds; D015032:Zinc