Fujimoto Hayato, Yamamura Shisato, Tobisu Mamoru
Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan.
Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, Suita, Osaka 565-0871, Japan.
J Am Chem Soc. 2025 Jul 2;147(26):22302-22308. doi: 10.1021/jacs.5c03980. Epub 2025 May 14.
Despite the widespread use of arynes in organic synthesis, their polymerization remains a significant challenge due to the intrinsic instability and short lifetime of aryne intermediates. Here, we report a method for aryne polymerization using a simple organonucleophile, -arylpyrazole, as an initiator. This polymerization proceeds via a unique pyrazole-induced nucleophilic aromatic substitution mechanism, facilitating the formation of poly(-arylene)s with narrow polydispersity and well-defined structures. The high chemical stability of -arylpyrazole allows for a broader scope of applications, including aryne polymerization at the side chain of preformed polymers (graft polymerization) and the synthesis of star-shaped poly(-arylene)s.
尽管芳炔在有机合成中得到广泛应用，但由于芳炔中间体固有的不稳定性和短寿命，其聚合仍然是一项重大挑战。在此，我们报道了一种使用简单有机亲核试剂——芳基吡唑作为引发剂进行芳炔聚合的方法。这种聚合反应通过独特的吡唑诱导亲核芳香取代机制进行，有助于形成具有窄多分散性和明确结构的聚（亚芳基）。芳基吡唑的高化学稳定性使其具有更广泛的应用范围，包括在预制聚合物侧链上进行芳炔聚合（接枝聚合）以及合成星形聚（亚芳基）。
