ORGN 675 |
| The epoxidation of olefins is an extremely important transformation from an industrial as well as an academic point of view. In this respect, especially the use of aqueous H2O2 as terminal oxidant has received considerable attention. For this reason the mechanism of the electrophilic activation of H2O2 by fluorinated alcohols as well as by arsonic acids has been investigated experimentally and theoretically with a high degree of correlation. In the case of the H2O2 activation by fluorinated alcohols, we have found multiple H-bond networks (1) responsible for the increased reactivity. In the arsonic acid-catalysis peracid intermediates (4 and 5) are likely to be be formed, which exhibit a high epoxidation potential. On the basis of these mechanistic insights we propose a new concept for the development of novel (organo-)catalysts for olefin epoxidation.
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Physical Organic Chemistry: Calculations, Mechanisms, Photochemistry, and High-Energy Species
1:00 PM-5:00 PM, Wednesday, 16 March 2005 Convention Center -- Room 11A, Oral
Division of Organic Chemistry |
