Department of Chemical Science and Engineering, Kobe University, 1-1 Rokkodai, Nada, Kobe 657-8501, Japan.
J Am Chem Soc. 2013 Aug 21;135(33):12208-11. doi: 10.1021/ja406374t. Epub 2013 Aug 9.
Revisiting Murahashi coupling, we found that it effectively allows polymerization of lithiated (hetero)arenes by nickel(II)-catalyzed polycondensation. Deprotonative polymerization of 2-chloro-3-substituted thiophene with n-butyllithium gave head-to-tail-type poly(3-substituted thiophene). Poly(1,4-arylene)s were obtained by the reaction of the corresponding dibromides through lithium-bromine exchange. A lithiated thiophene derivative obtained via deprotonative halogen dance also underwent polymerization to afford a bromo-substituted polythiophene.
重新审视 Murahashi 偶联反应，我们发现它可以通过镍（II）催化的缩聚有效地引发锂化（杂）芳环的聚合。用正丁基锂对 2-氯-3-取代噻吩进行脱质子聚合，得到头-尾型聚（3-取代噻吩）。通过锂-溴交换反应，相应的二溴化物反应得到聚（1,4-亚芳基）。通过脱质子卤代舞获得的锂化噻吩衍生物也进行了聚合，得到了溴取代的聚噻吩。
