Dou Bowen, Xu Yan, Wang Jianbo
Beijing National Laboratory of Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China.
The State Key Laboratory of Organometallic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China.
J Am Chem Soc. 2023 May 10;145(18):10422-10430. doi: 10.1021/jacs.3c03069. Epub 2023 May 1.
Modification of commodity aromatic polymers is highly desirable for accessing materials with new properties. The long-standing challenge for such approaches lies in the development of catalytic methods that can functionalize the aromatic polymers with high precision while preserving the molecular weight and distribution of the starting polymers without any alteration. Herein, we report a highly efficient AuCl-catalyzed site-selective aromatic C-H halogenation of polystyrene. The most important feature of this method is that the degree of halogenation can be precisely controlled by simply changing the loading of the halogenating agent, thus allowing the tuning of functional group density in an accurate and predictable manner. Various functional groups, including NH and Bpin, can be installed through effective derivatization of the resultant brominated polystyrene, thus making the method a valuable strategy for the synthesis of value-added materials with tailored properties.
对商品芳香族聚合物进行改性非常有助于获得具有新性能的材料。此类方法长期面临的挑战在于开发催化方法，该方法能够在不改变起始聚合物的分子量和分布的情况下，高精度地使芳香族聚合物官能化。在此，我们报道了一种高效的AuCl催化的聚苯乙烯位点选择性芳香C-H卤化反应。该方法最重要的特点是，通过简单改变卤化剂的用量就可以精确控制卤化程度，从而能够以准确且可预测的方式调节官能团密度。通过对所得溴化聚苯乙烯进行有效的衍生化反应，可以引入包括NH和Bpin在内的各种官能团，因此该方法是合成具有定制性能的增值材料的一种有价值的策略。
