Enantioselective Resolution Copolymerization of Racemic cis-Epoxides and Cyclic Anhydrides Mediated by Multichiral Bimetallic Chromium Complexes,Macromolecules

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Enantioselective Resolution Copolymerization of Racemic cis-Epoxides and Cyclic Anhydrides Mediated by Multichiral Bimetallic Chromium Complexes
Macromolecules ( IF 5.1 ) Pub Date : 2022-05-10 , DOI: 10.1021/acs.macromol.2c00628
Guang-Hui He ₁ , Yan-Lan Liu ₁ , Ye Liu ₁ , Xiao-Bing Lu ₁

Affiliation

Enantioselective resolution copolymerization of racemic epoxides is a powerful strategy for the production of optically active polymers with main-chain chirality and highly enantioenriched epoxides. However, a deep investigation on unsymmetrically disubstituted cis-epoxides for the preparation of chiral polymers is scanty because of their limited reactivity and complex regio- and stereo-selectivity. In this contribution, we report the highly enantioselective resolution copolymerization of racemic cis-disubstituted epoxides with cyclic anhydrides mediated by multichiral bimetallic chromium complexes. Up to 36 examples of cis-disubstituted epoxides, including conjugated alicyclic epoxides, aliphatic epoxides, aromatic epoxides, and ether-containing epoxides, were employed to the enantioselective copolymerization with cyclic anhydrides under mild conditions. Optically active polyesters with enantiomeric excess (ee) up to 96% were obtained, while unreacted enantiopure epoxides were isolated with up to 97% ee. The steric hindrance and electronic properties of the substituent groups in the epoxide monomers considerably affect the regioselectivity during the ring-opening process. The diverse structures of cis-disubstituted epoxides are beneficial for preparing various chiral copolymers with excellent functionality and tunable properties.

中文翻译：

多手性双金属铬配合物介导外消旋顺式环氧化物和环酐的对映选择性拆分共聚

外消旋环氧化物的对映选择性拆分共聚是生产具有主链手性和高度对映富集环氧化物的光学活性聚合物的有力策略。然而，由于其有限的反应性和复杂的区域和立体选择性，对用于制备手性聚合物的不对称二取代顺式环氧化物的深入研究很少。在此贡献中，我们报告了由多手性双金属铬配合物介导的外消旋顺式二取代环氧化物与环状酸酐的高度对映选择性拆分共聚。多达 36 个顺式示例-二取代环氧化物，包括共轭脂环族环氧化物、脂肪族环氧化物、芳族环氧化物和含醚环氧化物，被用于在温和条件下与环酐进行对映选择性共聚。获得了对映体过量 (ee) 高达 96% 的光学活性聚酯，而分离出的未反应的对映体纯环氧化物高达 97% ee。环氧化物单体中取代基的空间位阻和电子性质显着影响开环过程中的区域选择性。顺式二取代环氧化物的多样化结构有利于制备各种具有优异功能和可调性能的手性共聚物。

更新日期：2022-05-10

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