Enantioselective Resolution Copolymerization of Racemic 2,3-Disubstituted cis-Epoxides with CO_(2) Mediated by Binuclear Cobalt(Ⅲ)Catalyst
有 CO2 的外消旋的 2,3-Disubstituted cis-Epoxides 的 Enantioselective 决定 Copolymerization 由 Binuclear 钴(III ) 催化剂调停了作者机构：State Key Laboratory of Fine ChemicalsDalian University of TechnologyDalianLiaoning 116024China
出 版 物：《Chinese Journal of Chemistry》 (中国化学（英文版）)
年 卷 期：2021年第39卷第9期
页 面：2386-2390页
核心收录：
学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学]
主 题：Asymmetric catalysis Internal c/s-epoxides Carbon dioxide fixation Polymerization Hammett constant
摘 要：Enan tioselective resoluti on copolymerization of racemic internal epoxides with carb on dioxide(CO_(2))is a challe nging issue because of their poor reactivity and complicated regio/***,we describe the first enantioselective resolution copolymeriza-tion of racemic aromatic 2,3-disubstituted c/s-epoxides and CO_(2) using enantiopure dinuclear cobalt(lll)complexes as catalyst under mild conditions,affordi ng the corresp on ding polycarbonates with completely alter nating structure and good enantioselectivity in the range of 70% to 97%*** isotactic polycarb on ate from/3-methylstyre ne oxide is a typical semicrystalli ne material,possessi ng a melting point of 241℃;while other isotactic-enriched copolymers from 2,3-disubstituted c/s-epoxides bearing a substitute group on the aromatic ring are amorphous,having glass transition temperatures between 86℃ and 124℃.Interestingly,the copolymer selectivity is correlated well with the Hammett substituent constant,and the highest polymer selectivity of 98%was found in the system using the epoxides bearing an electron-donating group on the benzene ring.
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