Wu Tianhong, Liang Tianyu, Hu Wei, Du Meiqing, Zhang Sijia, Zhang Yanfeng, Anslyn Eric V, Sun Xiaolong
The Key Laboratory of Biomedical Information Engineering of Ministry of Education, School of Life Science and Technology, Xi'an Jiaotong University, Xi'an 710049, P. R. China.
College of Bioresources and Materials Engineering, Shaanxi University of Science & Technology, Xi'an, Shaanxi 710021, P. R. China.
ACS Macro Lett. 2021 Sep 21;10(9):1125-1131. doi: 10.1021/acsmacrolett.1c00548. Epub 2021 Aug 31.
In this Letter, we report that two amines can be coupled together rapidly and quantitatively through amine-thiol scrambling using a bisvinylogous thioester conjugate acceptor under mild conditions. The resulting bisvinylogous amide conjugate acceptors can be decoupled via an ethylene diamine-induced cyclization. Four representative conjugate acceptors have been utilized in the couple-decouple reactions, which were monitored and characterized by nuclear magnetic resonance, high-resolution mass spectrometry, and UV-vis spectroscopy. Further, we applied these small-molecule-based "click-declick" reactions to polymer synthesis and degradation. Highly cross-linked polymers, i.e., plastics, were quantitatively synthesized by simple reactions between commercial tris(2-aminoethyl)amine and the conjugate acceptors without solvent and any initiator or catalyst through ball milling within 60 min. Significantly, these thermosetting plastics can be degraded within 3-24 h via addition of ethylene diamine. The multiple architectures, application to plastics synthesis, and chemically triggered clean degradation to the thermosets at mild conditions with little input of energy herald a new generation of "intelligent" materials.
在本信函中，我们报告了在温和条件下，使用双烯醇式硫酯共轭受体通过胺 - 硫醇交换反应可使两种胺快速且定量地偶联在一起。所得的双烯醇式酰胺共轭受体可通过乙二胺诱导的环化反应解偶联。四种代表性的共轭受体已用于偶联 - 解偶联反应，通过核磁共振、高分辨率质谱和紫外 - 可见光谱对其进行监测和表征。此外，我们将这些基于小分子的“点击 - 脱点击”反应应用于聚合物的合成与降解。通过商业用三（2 - 氨基乙基）胺与共轭受体之间在无溶剂、无任何引发剂或催化剂的情况下，于60分钟内通过球磨进行简单反应，定量合成了高度交联的聚合物，即塑料。值得注意的是，通过添加乙二胺，这些热固性塑料可在3 - 24小时内降解。多种结构、在塑料合成中的应用以及在温和条件下以极少的能量输入对热固性材料进行化学触发的清洁降解，预示着新一代“智能”材料的诞生。
