Tandem diaza-Cope rearrangement polymerization: turning intramolecular reaction into powerful polymerization to give enantiopure materials for Zn2+ sensors,Chemical Science

当前位置： X-MOL 学术 › Chem. Sci. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Tandem diaza-Cope rearrangement polymerization: turning intramolecular reaction into powerful polymerization to give enantiopure materials for Zn2+ sensors
Chemical Science ( IF 7.6 ) Pub Date : 2020-12-8 , DOI: 10.1039/d0sc06138g
Soon-Hyeok Hwang ₁ , Tae-Lim Choi ₁

Affiliation

[3,3]-Sigmatropic rearrangement is a powerful reaction to form C–C bonds stereospecifically; however, owing to intrinsic simultaneous bond formation and breakage, this versatile method has not been utilized in polymerization. Herein, we report a new tandem diaza-Cope rearrangement polymerization (DCRP) that can synthesize polymers with defect-free C–C bond formation from easy and efficient imine formation. A mechanistic investigation by in situ ¹H NMR experiments suggests that this polymerization proceeds by a rapid DCR process, forming an enantiospecific C–C bond that occurs almost simultaneously with imine formation. This polymerization produces not only highly stable polymers against hydrolysis due to resonance-assisted hydrogen bonds (RAHBs) but also chiral polymers containing enantiopure salen moieties, which lead to high-performance Zn²⁺-selective turn-on chemosensors with up to 73-fold amplification. We also found that their optical activities and sensing performances are heavily dependent on the reaction temperature, which significantly affects the stereoselectivity of DCR.

中文翻译：

Tandem diaza-Cope 重排聚合：将分子内反应转化为强大的聚合，为 Zn2+ 传感器提供对映体纯材料

[3,3]-Sigmatropic 重排是立体定向形成 C–C 键的强大反应；然而，由于内在的同时键形成和断裂，这种通用方法尚未用于聚合。在此，我们报告了一种新的串联二氮杂-Cope重排聚合（DCRP），它可以通过简单有效的亚胺形成合成具有无缺陷C-C键形成的聚合物。原位机械研究¹H NMR 实验表明，这种聚合反应通过快速 DCR 过程进行，形成对映体特异性 C-C 键，该键几乎与亚胺形成同时发生。由于共振辅助氢键 (RAHB)，这种聚合反应不仅产生了高度稳定的聚合物，而且还产生了含有对映纯salen 部分的手性聚合物，从而产生了高达 73 倍的高性能 Zn ²⁺选择性开启化学传感器放大。我们还发现它们的光学活性和传感性能在很大程度上取决于反应温度，这显着影响了 DCR 的立体选择性。

更新日期：2020-12-23

点击分享查看原文

点击收藏

公开下载

阅读更多本刊新发论文本刊介绍/投稿指南