Alkyne Polymers from Stable Butatriene Homologues: Controlled Radical Polymerization of Vinylidenecyclopropanes,Journal of the American Chemical Society

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Alkyne Polymers from Stable Butatriene Homologues: Controlled Radical Polymerization of Vinylidenecyclopropanes
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-01-23 , DOI: 10.1021/jacs.2c12220
Bin Wu ₁ , Qian-Jun Ding ₁ , Zheng-Lin Wang ₁ , Rong Zhu ₁

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Controlled polymerization of cumulenic monomers represents a promising yet underdeveloped strategy toward well-defined alkyne polymers. Here we report a stereoelectronic effect-inspired approach using simple vinylidenecyclopropanes (VDCPs) as butatriene homologues in controlled radical ring-opening polymerizations. While being thermally stable, VDCPs mimic butatrienes via conjugation of the cyclopropane ring. This leads to exclusive terminal-selective propagation that affords a highly structurally regular alkyne-based backbone, featuring complete ring-opening and no backbiting regardless of polymerization conditions.

中文翻译：

来自稳定的丁三烯同系物的炔烃聚合物：亚乙烯基环丙烷的受控自由基聚合

累积单体的受控聚合代表了一种有前途但尚未开发的明确定义的炔烃聚合物的策略。在这里，我们报告了一种受立体电子效应启发的方法，使用简单的亚乙烯基环丙烷 (VDCP) 作为受控自由基开环聚合中的丁三烯同系物。虽然具有热稳定性，但 VDCP 通过环丙烷环的共轭来模拟丁三烯。这导致了独特的末端选择性传播，提供了结构高度规则的基于炔烃的主链，无论聚合条件如何，都具有完全开环和无背咬的特点。

更新日期：2023-01-23

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