The Acid Hydrolysis Mechanism of Acetals Catalyzed by a Supramolecular Assembly in Basic Solution [electronic resource]
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Online Access |
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| Format: | Government Document Electronic eBook |
| Language: | English |
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Berkeley, Calif. : Oak Ridge, Tenn. :
Lawrence Berkeley National Laboratory ; distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy,
2008.
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| Abstract: | A self-assembled supramolecular host catalyzes the hydrolysis of acetals in basic aqueous solution. The mechanism of hydrolysis is consistent with the Michaelis-Menten kinetic model. Further investigation of the rate limiting step of the reaction revealed a negative entropy of activation (ΔS{double_dagger} = -9 cal mol⁻¹K⁻¹) and an inverse solvent isotope effect (k(H₂O)/k(D₂O) = 0.62). These data suggest that the mechanism of hydrolysis that takes place inside the assembly proceeds through an A-2 mechanism, in contrast to the A-1 mechanism operating in the uncatalyzed reaction. Comparison of the rates of acetal hydrolysis in the assembly with the rate of the reaction of unencapsulated substrates reveals rate accelerations of up to 980 over the background reaction for the substrate diethoxymethane. |
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| Item Description: | Published through the Information Bridge: DOE Scientific and Technical Information. 09/24/2008. "lbnl-1575e" Journal of Organic Chemistry ISSN 0022-3263; JOCEAH FT. Raymond, Kenneth N.; Bergman, Robert G.; Pluth, Michael D. Chemical Sciences Division. |