Dynamic Covalent Chemistry
Published Online: 15 MAR 2012
Copyright © 2012 John Wiley & Sons, Ltd. All rights reserved.
Supramolecular Chemistry: From Molecules to Nanomaterials
How to Cite
Gasparini, G., Dal Molin, M., Lovato, A. and Prins, L. J. 2012. Dynamic Covalent Chemistry. Supramolecular Chemistry: From Molecules to Nanomaterials.
- Published Online: 15 MAR 2012
Dynamic covalent chemistry forms the key ingredient for a new approach toward organic synthesis. Dynamic covalent chemistry regards the synthesis of covalent organic molecules under thermodynamic control. It relies on the use of covalent bonds that can be reversibly formed under the experimental conditions. It combines the advantages typically associated with noncovalent synthesis (the formation of molecular structures using noncovalent interactions), such as spontaneous formation, error correction, and proof reading, with the robustness of covalent bonds. For many covalent bonds, experimental conditions under which the reaction occurs reversibly are known, but the majority of systems relies on trans(thio)esterifications and disulfide or imine-type exchange reactions. These reactions occur rapidly under mild conditions, use readily accessible building blocks, and can be turned off to obtain kinetically inert products. It is illustrated that dynamic covalent chemistry gives a rapid access toward organic structures of nanometer dimensions. Typically, a one-step, one-pot synthetic protocol is used, which in some cases also involves multiple dynamic covalent bonds in an orthogonal manner. The fundamental difference with covalent synthesis is that equilibrium reactions are used. This introduces a characteristic property, which is the possibility of the chemical system to adapt to changes in its environment according to Le Châtelier's principle. This concept is referred to as dynamic combinatorial chemistry (DCC) and has been successfully applied for the preparation of new receptors, guests, sensors, materials, and so forth. Examples, together with the potential and limitations of this approach, are discussed. The final section is dedicated to the systems in which dynamic covalent bonds provide structural stability but intramolecular noncovalent interactions determine the composition of the resulting equilibrium. It is shown that this approach, that is, dynamic covalent capture, is a very sensitive tool for the quantification of weak interactions, for instance, in protein folding or catalysis.
- dynamic covalent bonds;
- thermodynamic control;
- dynamic combinatorial chemistry;
- dynamic covalent capture;
- organic nanostructures