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- W3147307575 abstract "1,2-trans-Glycosides hydrolyze through different mechanisms at different pH values, but systematic studies are lacking. Here, we report the pH–rate constant profile for the hydrolysis of 4-nitrophenyl β-D-glucoside. An inverse kinetic isotope effect of k(H3O+)/k(D3O+) = 0.65 in the acidic region indicates that the mechanism requires the formation of the conjugate acid of the substrate for the reaction to proceed, with the heterolytic cleavage of the glycosidic C–O bond. Reactions in the pH-independent region exhibit general catalysis with a single proton in flight, a normal solvent isotope effect of kH/kD = 1.5, and when extrapolated to zero buffer concentration show a small solvent isotope effect of k(H2O)/k(D2O) = 1.1, consistent with water attack through a dissociative mechanism. In the basic region, solvolysis in 18O-labeled water and H2O/MeOH mixtures allowed the detection of bimolecular hydrolysis and neighboring group participation, with a minor contribution of nucleophilic aromatic substitution. Under mildly basic conditions, a bimolecular concerted mechanism is implicated through an inverse solvent isotope effect of k(HO–)/k(DO–) = 0.5 and a strongly negative entropy of activation (ΔS‡ = −13.6 cal mol–1 K–1). Finally, at high pH, an inverse solvent isotope effect of k(HO–)/k(DO–) = 0.5 indicates that the formation of 1,2-anhydrosugar is the rate-determining step." @default.
- W3147307575 created "2021-04-13" @default.
- W3147307575 creator A5021413336 @default.
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- W3147307575 date "2021-06-30" @default.
- W3147307575 modified "2023-10-15" @default.
- W3147307575 title "Unimolecular, Bimolecular, and Intramolecular Hydrolysis Mechanisms of 4-Nitrophenyl β-<scp>d</scp>-Glucopyranoside" @default.
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- W3147307575 doi "https://doi.org/10.1021/acs.joc.1c00836" @default.
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