Acid Catalysis in Basic Solution: A Supramolecular Host Promotes Orthoformate Hydrolysis
Top Cited Papers
- 6 April 2007
- journal article
- other
- Published by American Association for the Advancement of Science (AAAS) in Science
- Vol. 316 (5821), 85-88
- https://doi.org/10.1126/science.1138748
Abstract
Although many enzymes can promote chemical reactions by tuning substrate properties purely through the electrostatic environment of a docking cavity, this strategy has proven challenging to mimic in synthetic host-guest systems. Here, we report a highly charged, water-soluble, metal-ligand assembly with a hydrophobic interior cavity that thermodynamically stabilizes protonated substrates and consequently catalyzes the normally acidic hydrolysis of orthoformates in basic solution, with rate accelerations of up to 890-fold. The catalysis reaction obeys Michaelis-Menten kinetics and exhibits competitive inhibition, and the substrate scope displays size selectivity, consistent with the constrained binding environment of the molecular host.Keywords
This publication has 27 references indexed in Scilit:
- Molecular Recognition and Stabilization of Iminium Ions in WaterJournal of the American Chemical Society, 2006
- Analysis of Host‐Assisted Guest Protonation Exemplified for p‐Sulfonatocalix[4]arene—Towards Enzyme‐Mimetic pKa ShiftsChemistry – A European Journal, 2006
- Diels-Alder in Aqueous Molecular Hosts: Unusual Regioselectivity and Efficient CatalysisScience, 2006
- Supramolecular Catalysis of Organic Reactions Involving CyclodextrinsAdvances in Organic Synthesis, 2005
- Selective C-H Bond Activation by a Supramolecular Host–Guest AssemblyAngewandte Chemie International Edition, 2004
- A Joint Structural, Kinetic, and Thermodynamic Investigation of Substituent Effects on Host−Guest Complexation of Bicyclic Azoalkanes by β-CyclodextrinJournal of the American Chemical Society, 2001
- Two Mechanisms of Slow Host-Guest Complexation between Cucurbit[6]uril and Cyclohexylmethylamine: pH-Responsive Supramolecular KineticsAngewandte Chemie International Edition, 2001
- Resolution and Kinetic Stability of a Chiral Supramolecular Assembly Made of Labile ComponentsAngewandte Chemie International Edition, 2001
- On the Evaluation of the Constants
V
m
and
K
M
in Enzyme ReactionsScience, 1952
- Acid catalysis in hydrolytic reactionsTransactions of the Faraday Society, 1929