Noordzij Geert J, Wilsens Carolus H R M
Chemelot InSciTe, Geleen, Netherlands.
Faculty of Science and Engineering, Aachen-Maastricht Institute of Biobased Materials (AMIBM), Maastricht University, Geleen, Netherlands.
Front Chem. 2019 Nov 14;7:729. doi: 10.3389/fchem.2019.00729. eCollection 2019.
Although the aza-Michael addition reaction on various unsaturated (di-)carboxylic acids and esters of, for example, itaconic acid, is well-known, the consecutive cyclization reaction has not received much attention in literature. The products of this aza-Michael cascade reaction, being mono- or di-carboxylic acid or ester functionalized -alkyl-pyrrolidone structures, prove interesting for melt-polycondensation reactions as they exhibit excellent stability at elevated temperatures. In other words, this reaction is a toolbox for the generation of renewable monomers and, in turn, polymers with tunable physiological properties. Therefore, this work provides an overview of the state-of-the-art of the cascade aza-Michael addition-cyclization reactions on biobased unsaturated acids and esters, and their use in polymerization reactions. Furthermore, we extend this overview with the cascade aza-Michael addition-cyclization reaction of -trimethyl aconitate with di-amines to form a tetra-functional -alkyl--(pyrrolidone dimethylcarboxylate), which exhibits excellent thermal stability and could effectively be used as monomer in polycondensation reactions. Importantly, the aza-Michael addition reaction between primary amines and -trimethyl aconitate can be considered a click-reaction; it proceeds quantitatively within minutes under ambient conditions and follows the principles of green chemistry.
尽管在各种不饱和（二）羧酸以及例如衣康酸的酯上进行氮杂迈克尔加成反应是众所周知的，但连续环化反应在文献中并未受到太多关注。这种氮杂迈克尔串联反应的产物，即单羧酸或二羧酸或酯官能化的烷基吡咯烷酮结构，因其在高温下表现出优异的稳定性，所以在熔融缩聚反应中很有吸引力。换句话说，该反应是生成可再生单体进而生成具有可调节生理特性聚合物的工具箱。因此，这项工作概述了基于生物的不饱和酸和酯上的氮杂迈克尔加成 - 环化串联反应的最新进展及其在聚合反应中的应用。此外，我们将柠檬酸三甲酯与二胺的氮杂迈克尔加成 - 环化串联反应纳入此概述，该反应生成具有优异热稳定性且可有效用作缩聚反应单体的四官能化烷基 -（吡咯烷酮二甲基羧酸酯）。重要的是，伯胺与柠檬酸三甲酯之间的氮杂迈克尔加成反应可被视为一种点击反应；它在环境条件下几分钟内即可定量进行，并且遵循绿色化学原则。
