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Olefin epoxidation by dioxiranes and percarboxylic acids: an analysis of activation energies calculated by a density functional method
Author(s) -
Gisdakis Philip,
Rösch Notker
Publication year - 2001
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.386
Subject(s) - chemistry , dioxirane , olefin fiber , hydrogen peroxide , hydrogen fluoride , homo/lumo , molecular orbital , density functional theory , medicinal chemistry , activation energy , atomic orbital , computational chemistry , proton , organic chemistry , catalysis , molecule , physics , quantum mechanics , electron
The activity of dioxiranes, R 2 CO 2 , and percarboxylic acids, RCO(O 2 )H, in olefin epoxidation reactions can be rationalized by a frontier orbital interaction. Barrier heights of these oxygen transfer reactions, as calculated by a density functional method, depend linearly on the energy of the olefin HOMO orbital π (C—C) and of the peroxide LUMO orbital σ*(O—O). Activation barriers can be predicted from linear relationships with the proton affinity of a dioxirane (as measured by the hydrogen fluoride association energy) or the p K a value of a percarboxylic acid. Copyright © 2001 John Wiley & Sons, Ltd.