title: Mechanistic implications of pseudo zero order kinetics in kinetic resolutions.
abstract: This work provides simulations as well as experimental results from kinetic resolutions to demonstrate that a constant product enantioselectivity versus conversion profile in kinetic resolution is not a general consequence of pseudo zero order kinetics in [substrate] but occurs only under specific mechanistic constraints. For such a profile to be observed, the reaction must follow a mechanism exhibiting saturation kinetics for only one enantiomeric [substrate] on the only one of the two parallel pathways. For a single catalyst species, this will be limited to situations of near-perfect selectivity. Combining kinetic profiles with the enantioselectivity/conversion relationship in kinetic resolution can help to distinguish between proposed mechanisms and provide information about relative binding constants, the reactivity of intermediate species, and turnover by more than one active catalyst species.
authors.affiliation: Department of Chemistry, Imperial College, London SW7 2AZ, UK. d.blackmond@imperial.ac.uk
authors.forename: Donna G
authors.initials: DG
authors.lastname: Blackmond
authors.forename: Neil S
authors.initials: NS
authors.lastname: Hodnett
authors.forename: Guy C
authors.initials: GC
authors.lastname: Lloyd-Jones
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D000475:Alkenes / Q000737:chemistry*; D001665:Binding Sites; D002384:Catalysis; D004852:Epoxy Compounds / Q000737:chemistry; D007700:Kinetics; D008670:Metals / Q000737:chemistry*; D008956:Models, Chemical; D010084:Oxidation-Reduction
chemical_list: D000438:Alcohols; D000475:Alkenes; D004852:Epoxy Compounds; D008670:Metals