title: Asymmetric catalysis of aldol reactions with chiral lewis bases.
abstract: In an extension of studies both on the stereochemical course of the aldol addition and on Lewis-base-catalyzed allylation reactions, we have invented a new Lewis-base-catalyzed asymmetric aldol addition. This Account outlines the conceptual development, the identification of design criteria, and the underlying principles for such a process. The reduction of these elements to practice in the demonstration of enantioselective aldol additions of trichlorosilyl enolates catalyzed by chiral phosphoramides is also presented. From a combination of stereochemical, kinetic, and structural studies, an intruiging mechanistic hypothesis is forwarded that explains the origin of catalysis and diastereoselectivity.
authors.affiliation: Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, Illinois 61801, USA.
authors.forename: S E
authors.initials: SE
authors.lastname: Denmark
authors.forename: R A
authors.initials: RA
authors.lastname: Stavenger
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D002384:Catalysis; D007659:Ketones / Q000737:chemistry*; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D009943:Organophosphorus Compounds / Q000737:chemistry; D012821:Silanes; D013237:Stereoisomerism
chemical_list: D000447:Aldehydes; D007659:Ketones; D009942:Organometallic Compounds; D009943:Organophosphorus Compounds; D012821:Silanes