Controlling the composition and sequence during diazo copolymerization with vinyl or acetylenic monomers is highly desired yet challenging. Here we report a new base-metal-catalysis strategy to address this problem via tandem coupling/polymerization. A selective Cu-catalyzed C(3+1) copolymerization reaction was developed using propargyl carbonates and aryldiazomethanes derived from N-tosylhydrazones as the C3 and C1 building blocks, respectively. This reaction rapidly produces alternating-like poly(1,4-diaryl-2-butyne-1,4-diyl)s (M_n up to 31.0 kg/mol) in a modular fashion, without detectable homopolymer segments. This work provides a new avenue for the synthesis of hydrocarbon polymers through diazo copolymerization.

在与乙烯基或炔属单体的重氮共聚过程中控制组成和顺序是非常需要但具有挑战性的。在这里，我们报告了一种新的贱金属催化策略，通过串联偶联/聚合来解决这个问题。选择性铜催化 C(3+1) 共聚反应是使用炔丙基碳酸酯和 aryldiazomethanes 衍生自N -tosylhydrazones 作为 C3 和 C1 结构单元，分别。该反应以模块化方式快速生成类似交替的聚 (1,4-diaryl-2-butyne-1,4-diyl)（M _n高达 31.0 kg/mol），没有可检测的均聚物片段。该工作为通过重氮共聚合成烃类聚合物提供了一条新途径。