title: Epoxidations by peracid anions in water: ambiphilic oxenoid reactivity and stereoselectivity.
abstract: [reaction: see text] Transition structures have been located for oxygen transfer from performate anion to ethylene, propene, vinylamine, vinyl chloride, vinyl cyanide, and 2-propen-1-ol at the B3LYP/6-31+G(d,p) level in a CPCM continuum model for water. Oxygen transfer is concerted, except for acrylonitrile, which is stepwise. Peracid anions react as ambiphilic oxygen donors. Predictions are made about the diastereoselectivity of epoxidations of acylic, chiral, and allylic alcohols in an alkaline solution, and one is verified experimentally.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles 90095-1569, USA.
authors.forename: Ilyas
authors.initials: I
authors.lastname: Washington
authors.forename: K N
authors.initials: KN
authors.lastname: Houk
mesh_terms: D000838:Anions / Q000737:chemistry*; D004852:Epoxy Compounds / Q000737:chemistry*; D013237:Stereoisomerism; D013816:Thermodynamics
chemical_list: D000838:Anions; D004852:Epoxy Compounds