Organocatalyzed and Uncatalyzed CC/CC and CC/CN Exchange Processes between Knoevenagel and Imine Compounds in Dynamic Covalent Chemistry |
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Authors: | Sirinan Kulchat Kamel Meguellati Jean‐Marie Lehn |
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Affiliation: | 1. Laboratoire de Chimie Supramoléculaire, Institut de Science et d'Ingénierie Supramoléculaires (ISIS), Université de Strasbourg, 8 allée Gaspard Monge, BP 70028, F‐67000 Strasbourg Cedex, (phone: +33?3?68?85?51?45;2. fax: +33?3?68?85?51?40);3. fax: +33?3?68?85?51?40)Laboratoire de Chimie Supramoléculaire, Institut de Science et d'Ingénierie Supramoléculaires (ISIS), Université de Strasbourg, 8 allée Gaspard Monge, BP 70028, F‐67000 Strasbourg Cedex, (phone: +33?3?68?85?51?45 |
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Abstract: | Molecular diversity generation through reversible component exchange has acquired great importance in the last decade with the development of dynamic covalent chemistry. We explore here the recombination of components linked by C?C and C?N bonds through reversible double‐bond formation, and cleavage in C?C/C?C and C?C/C?N exchange processes. The reversibility of the Knoevenagel reaction has been explored, and C?C/C?C C/C exchanges have been achieved among different benzylidenes, under organocatalysis by secondary amines such as L ‐proline. The substituents of these benzylidenes were shown to play a very important role in the kinetics of the exchange reactions. L ‐Proline is also used to catalyze the reversible C?C/C?C exchange between Knoevenagel derivatives of barbituric acid and malononitrile. Finally, the interconversion between Knoevenagel derivatives of dimethylbarbituric acid and imines (C?C/C?N exchange) has been studied and was found to occur rapidly in the absence of catalyst. The results of this study pave the way for the extension of dynamic combinatorial chemistry based on C?C/C?C and C?C/C?N exchange systems. |
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Keywords: | Covalent dynamic libraries Organocatalysis Knoevenagel compounds Imines |
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