Wang Rong, Zhang Jie, Wan Xinhua
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, P. R. China.
Chem Rec. 2015 Apr;15(2):475-94. doi: 10.1002/tcr.201402083. Epub 2015 Jan 21.
Helical vinyl aromatic polymers are emerging as interesting chiral materials due to their dynamic tailorability, synthetic simplicity, and outstanding chemical and physical stabilities. This Personal Account discusses long-range chirality transfer in the radical polymerization of vinylterphenyl monomers and tunable stereomutation of the resultant polymers. It begins with a general introduction to the design, synthesis, and characterization of helical poly{(+)-2,5-bis[4'-((S)-2-methylbutyloxy)phenyl]styrene}, the first one of this series of polymers. Then, long-range chirality transfer during radical polymerization of terphenyl-based vinyl monomers is explained. After that, the chiroptical property control of the resultant polymers by means of the transition from kinetically controlled conformation to thermodynamically controlled conformation and external stimulus is described. This Personal Account concludes by discussing the advantages and disadvantages of the strategy of using vinylterphenyls to obtain optically active helical polymers and providing a short outlook, especially emphasizing the importance of tacticity on the chiroptical properties of polymers.
由于其动态可定制性、合成简便性以及出色的化学和物理稳定性，螺旋状乙烯基芳族聚合物正成为引人关注的手性材料。本个人述评讨论了乙烯基三联苯单体自由基聚合中的远程手性转移以及所得聚合物的可调谐立体异构化。首先对螺旋状聚{（+）-2,5-双[4'-（（S）-2-甲基丁氧基）苯基]苯乙烯}（该系列聚合物中的首个聚合物）的设计、合成和表征进行了一般性介绍。然后，解释了三联苯基乙烯基单体自由基聚合过程中的远程手性转移。之后，描述了通过从动力学控制构象向热力学控制构象的转变以及外部刺激来控制所得聚合物的手性光学性质。本个人述评最后讨论了使用乙烯基三联苯获得光学活性螺旋聚合物策略的优缺点，并给出了简短展望，特别强调了立构规整度对聚合物手性光学性质的重要性。
