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Hydrogen bonding effects in the epoxidation of propenol with dioxiranes. A DFT computational study

✍ Scribed by Mauro Freccero; Remo Gandolfi; Mirko Sarzi-Amadè; Augusto Rastelli

Publisher
Elsevier Science
Year
1998
Tongue
French
Weight
937 KB
Volume
54
Category
Article
ISSN
0040-4020

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✦ Synopsis

Potential energy surfaces for the epoxidations of 2-propen-l-ol with dioxirane (DHD) and dimethyldioxirane (DMD) were investigated at the B3LYP/6-3IG* level. Seven transition structures (TSs) were located for the reaction of DI-ID. The four chemically more significant TSs were located also for the reaction of DMD, Geometries and energies of two of them clearly demonstrate that stabilizing hydrogen bonding interactions can be at work and that they involve both the dioxirane oxygens. Calculations indicate that the electron attracting effect of the allylic hydroxy group has a relatively small rate retarding effect. Calculations predict higher reactivity for propenoi with respect to propene reaction in gas phase but introduction of electrostatic soivation effects (acetone. Tomasi model) leads to re, activity reversal in substantial agreement with experimental data.

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