Epoxidations by peracid anions in water: ambiphilic oxenoid reactivity and stereoselectivity.
[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.
Washington
Ilyas
I
Department of Chemistry and Biochemistry, University of California, Los Angeles 90095-1569, USA.
Houk
K N
KN
D000838:Anions / Q000737:chemistry*; D004852:Epoxy Compounds / Q000737:chemistry*; D013237:Stereoisomerism; D013816:Thermodynamics
D000838:Anions; D004852:Epoxy Compounds