title: Stereoelectronic, torsional, and steric effects on rates of enolization of ketones.
abstract: The stereoselectivities of base-catalyzed enolizations of ketones have been studied by quantum mechanical methods. Transition structures of exo and endo deprotonation of camphor, norcamphor, and dehydronorcamphor have been located with two model bases. Stereoelectronic, torsional, and steric effects on activation energies were assessed. These calculations demonstrate the importance of torsional strain between partial bonds and vicinal bonds on the rates of deprotonation and on related reactions involving the formation of enolates or reactions of enols and enolates.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, USA.
authors.forename: S M
authors.initials: SM
authors.lastname: Behnam
authors.forename: S E
authors.initials: SE
authors.lastname: Behnam
authors.forename: K
authors.initials: K
authors.lastname: Ando
authors.forename: N S
authors.initials: NS
authors.lastname: Green
authors.forename: K N
authors.initials: KN
authors.lastname: Houk
mesh_terms: D002384:Catalysis; D007659:Ketones / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D013237:Stereoisomerism
chemical_list: D007659:Ketones