Theoretical study of the reaction mechanism of the uncatalyzed epoxidation of alkenes by iodosylbenzeneElectronic supplementary information (ESI) available: B3LYP optimized geometries (Cartesian coordinates) and total energies for compounds 1 to 9. See http://www.rsc.org/suppdata/nj/b2/b203861g/

Abstract

The origin of the barrier for the uncatalyzed epoxidation of alkenes by iodosylbenzene is examined from a computational point of view. The reaction of a monomeric unit with ethylene presents a very low barrier, in disagreement with experimental data indicating the requirement of a catalyst. The polymeric structure of iodosylbenzene was then analyzed and the importance of the presence of a terminal hydration water in its linear structure confirmed. The reaction of a model dimer with ethylene is shown to have a high barrier, in good agreement with experiment. Implications of this result with respect to the nature of the catalytic mechanism are briefly discussed.