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Kulchat S, Chaur MN, Lehn JM. Kinetic Selectivity and Thermodynamic Features of Competitive Imine Formation in Dynamic Covalent Chemistry. Chemistry. 2017;23(46):11108-11118doi: 10.1002/chem.201702088.
Kulchat, S., Chaur, M. N., & Lehn, J. M. (2017). Kinetic Selectivity and Thermodynamic Features of Competitive Imine Formation in Dynamic Covalent Chemistry. Chemistry (Weinheim an der Bergstrasse, Germany), 23(46), 11108-11118. https://doi.org/10.1002/chem.201702088
Kulchat, Sirinan, et al. "Kinetic Selectivity and Thermodynamic Features of Competitive Imine Formation in Dynamic Covalent Chemistry." Chemistry (Weinheim an der Bergstrasse, Germany) vol. 23,46 (2017): 11108-11118. doi: https://doi.org/10.1002/chem.201702088
Kulchat S, Chaur MN, Lehn JM. Kinetic Selectivity and Thermodynamic Features of Competitive Imine Formation in Dynamic Covalent Chemistry. Chemistry. 2017 Aug 16;23(46):11108-11118. doi: 10.1002/chem.201702088. Epub 2017 Jul 26. PMID: 28628248.
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Chemistry. 2017 Aug 16;23(46):11108-11118. doi: 10.1002/chem.201702088. Epub 2017 Jul 26.

Kinetic Selectivity and Thermodynamic Features of Competitive Imine Formation in Dynamic Covalent Chemistry.

Chemistry (Weinheim an der Bergstrasse, Germany)

Sirinan Kulchat, Manuel N Chaur, Jean-Marie Lehn

Affiliations

  1. Laboratoire de Chimie Supramoléculaire, Institut de Science et d'Ingénierie Supramoléculaires (ISIS), Université de Strasbourg, 8 allée Gaspard Monge, BP 70028, 67000, Strasbourg Cedex, France.
  2. Materials Chemistry Research Unit, Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Khon Kaen University, Nai Muang, Muang, Khon Kaen, 40002, Thailand.
  3. Departamento de Química, Universidad del Valle, Cali, Colombia.

PMID: 28628248 DOI: 10.1002/chem.201702088

Abstract

The kinetic and thermodynamic selectivities of imine formation have been investigated for several dynamic covalent libraries of aldehydes and amines. Two systems were examined, involving the reaction of different types of primary amino groups (aliphatic amines, alkoxy-amines, hydrazides and hydrazines) with two types of aldehydes, sulfobenzaldehyde and pyridoxal phosphate in aqueous solution at different pD (5.0, 8.5, 11.4) on one hand, 2-pyridinecarboxaldehyde and salicylaldehyde in organic solvents on the other hand. The reactions were performed separately for given amine/aldehyde pairs as well as in competitive conditions between an aldehyde and a mixture of amines. In the latter case, the time evolution of the dynamic covalent libraries generated was followed, taking into consideration the operation of both kinetic and thermodynamic selectivities. The results showed that, in aqueous solution, the imine of the aliphatic amine was not stable, but oxime and hydrazone formed well in a pH dependent way. On the other hand, in organic solvents, the kinetic product was the imine derived from an aliphatic amine and the thermodynamic products were oxime and hydrazone. The insights gained from these experiments provide a basis for the implementation of imine formation in selective derivatization of mono-amines in mixtures as well as of polyfunctional compounds presenting different types of amino groups. They may in principle be extended to other dynamic covalent chemistry systems.

© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Keywords: dynamic covalent chemistry; imine formation; kinetic selectivity; thermodynamic

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