Synthesis of an optically active polymer containing a planar phthalimide backbone by asymmetric polymerization,Polymer Chemistry

当前位置： X-MOL 学术 › Polym. Chem. › 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.)

Synthesis of an optically active polymer containing a planar phthalimide backbone by asymmetric polymerization
Polymer Chemistry ( IF 4.1 ) Pub Date : 2020-09-02 , DOI: 10.1039/d0py01073a
Naoya Kanbayashi _{1,

2,

3,

4,

5} , Marina Saegusa _{1,

2,

3,

4,

5} , Yuki Ishido _{1,

2,

3,

4,

5} , Taka-aki Okamura _{1,

2,

3,

4,

5} , Kiyotaka Onitsuka _{1,

2,

3,

4,

5}

Affiliation

Asymmetric polymerization is a promising method for constructing sophisticated backbones that contain asymmetric carbons on the main chain. Herein, we report the precise design and synthesis of a novel polymer backbone that induces a helical structure through asymmetric polymerization reactions of a phthalimide-based monomer catalyzed by a planar-chiral cyclopentadienyl–ruthenium complex. When sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate was used as an additive, the polymerization proceeded with high regio- and enantioselectivity, producing an optically active polymer composed of a planar phthalimide backbone with enantiomerically enriched asymmetric carbons on the main chain. The terminal olefin in each monomer unit of the polymer could take on various substituents through thiol–ene reactions. CD and UV spectroscopic methods and conformational studies showed that the planar phthalimide backbones are tightly folded according to the local conformation determined by the two torsion angles around the asymmetric carbons of the main chain, resulting in the construction of a cylindrical 4₁-helical structure in solution, which was stable in polar solvents due to the solvophobic effect on the phthalimide backbones.

中文翻译：

通过不对称聚合合成包含平面邻苯二甲酰亚胺骨架的旋光聚合物

不对称聚合是一种有前途的方法，可用于构建在主链上包含不对称碳原子的复杂主链。在这里，我们报告了一种新型聚合物主链的精确设计和合成，该聚合物主链通过平面手性环戊二烯基-钌络合物催化的邻苯二甲酰亚胺基单体的不对称聚合反应诱导螺旋结构。当使用四[3,5-双（三氟甲基）苯基]硼酸钠作为添加剂时，聚合反应具有很高的区域选择性和对映选择性，从而生产出一种由平面邻苯二甲酰亚胺骨架构成的光学活性聚合物，该骨架上的对映体富含不对称碳原子。链。聚合物每个单体单元中的末端烯烃可以通过硫醇-烯反应接受各种取代基。溶液中的₁螺旋结构，由于对邻苯二甲酰亚胺主链的疏溶剂作用，在极性溶剂中稳定。

更新日期：2020-10-13

点击分享查看原文

点击收藏

阅读更多本刊最新论文本刊介绍/投稿指南11