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For the catalytic epoxidation by the do-transition metal catalysts, the oxidation states of the metal centers are not changed during the catalysis. The metal centers function as Lewis acids by withdrawing electrons from the O-O bond and thus increasing the electrophilic character of the coordinated peroxide. Active catalysts are the metal centers with strong Lewis acidity, (a) Thiel, W. R.; Eppinger, J Chem - Eur. J. 1997, 3, 696.
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The epoxidation of 3-methyl-3-butenyl acetate gave the corresponding epoxide in 13% yield under the same reaction conditions as those in Table 1. The yield for the acetate derivative was much lower than that (84%) for the homoallylic alcohol la, suggesting that the hydroxyl functionality plays an important role in the present epoxidation.
-
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79
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70349163148
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2 at 233 K showed a broad signal of the OH hydrogen at 1.91 ppm. Upon addition of one equivalent I (33 mM) with respect to la at 233 K, the broad signal was observed at 2.03 ppm. The downfield shift of la in the presence of I indicates the hydrogen bonding between I and la since the downfield shift of the OH hydrogen by the presence of the hydrogen bonding has been reported.
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The electron-withdrawing substituents decrease the electron density of the C=C double bond and reduce the π(C=C) HOMO energy, resulting in the decrease of the reactivity of the olefin with electrophilic oxidants.
-
The electron-withdrawing substituents decrease the electron density of the C=C double bond and reduce the π(C=C) HOMO energy, resulting in the decrease of the reactivity of the olefin with electrophilic oxidants.
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Cyclooctene was used as a model substrate to estimate the true oxygen transfer ability of the peroxotungstates without the hydrogen-bonding interaction between substrate and catalyst.
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