Kulchat Sirinan, Chaur Manuel N, Lehn Jean-Marie
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.
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.
Chemistry. 2017 Aug 16;23(46):11108-11118. doi: 10.1002/chem.201702088. Epub 2017 Jul 26.
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.
针对醛和胺的几个动态共价文库，研究了亚胺形成的动力学和热力学选择性。考察了两个体系，一方面是不同类型的伯氨基（脂肪胺、烷氧基胺、酰肼和肼）与两种醛，即磺基苯甲醛和磷酸吡哆醛在不同pD值（5.0、8.5、11.4）的水溶液中的反应；另一方面是2-吡啶甲醛和水杨醛在有机溶剂中的反应。对给定的胺/醛对分别进行反应，以及在醛与胺混合物的竞争条件下进行反应。在后一种情况下，跟踪生成的动态共价文库的时间演变，同时考虑动力学和热力学选择性的作用。结果表明，在水溶液中，脂肪胺的亚胺不稳定，但肟和腙能以pH依赖的方式良好形成。另一方面，在有机溶剂中，动力学产物是脂肪胺衍生的亚胺，热力学产物是肟和腙。从这些实验中获得的见解为在混合物中单胺以及具有不同类型氨基的多官能化合物的选择性衍生化中实施亚胺形成提供了基础。原则上，它们可扩展到其他动态共价化学体系。
