Controlled Living Cascade Polymerization of Polycyclic Enyne Monomers: Leveraging Complete Degradability for a Stereochemical and Structural Investigation,Journal of the American Chemical Society

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Controlled Living Cascade Polymerization of Polycyclic Enyne Monomers: Leveraging Complete Degradability for a Stereochemical and Structural Investigation
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2022-08-12 , DOI: 10.1021/jacs.2c05721
Antonio Rizzo ₁ , Eunsong Jung ₁ , Hojoon Song ₁ , Yunhyeong Cho ₁ , Gregory I Peterson ₂ , Tae-Lim Choi ₁

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Cascade polymerizations recently gained significant attention due to their use of unique transformations, involving multiple bond making and/or breaking steps, when converting monomers to repeat units. However, designing complex cascade polymerizations which proceed in a controlled manner is very challenging. Various side reactions can hamper polymerization performance and the efficiency of the cascade. In this work, we explore a metathesis-based cascade polymerization of unique polycyclic enyne monomers, which contain a terminal alkyne and two cyclic alkenes. By modifying the monomer’s stereochemistry, linkers, and ring types, we were able to modulate the polymerization performance and the extent to which a complete cascade reaction occurs. Upon subjecting the resulting polymers to mild acidic conditions and analyzing the degradation products, we were able to calculate the percentage of repeat units derived from a complete cascade reaction (termed the cascade efficiency). In addition to identifying how various structural parameters in the monomer influence the success of a cascade polymerization, we were able to achieve controlled living cascade polymerizations of multiple monomers with >99% cascade efficiency and produce various block copolymers.

中文翻译：

多环烯炔单体的可控活性级联聚合：利用完全降解性进行立体化学和结构研究

级联聚合最近由于在将单体转化为重复单元时使用了独特的转变而引起了极大的关注，包括多个键形成和/或断裂步骤。然而，设计以受控方式进行的复杂级联聚合是非常具有挑战性的。各种副反应会妨碍聚合性能和级联效率。在这项工作中，我们探索了基于复分解的独特多环烯单体的级联聚合，该单体包含一个末端炔烃和两个环状烯烃。通过修改单体的立体化学、接头和环类型，我们能够调节聚合性能和发生完整级联反应的程度。在将所得聚合物置于温和酸性条件下并分析降解产物后，我们能够计算来自完整级联反应的重复单元的百分比（称为级联效率）。除了确定单体中的各种结构参数如何影响级联聚合的成功之外，我们还能够以 >99% 的级联效率实现多种单体的可控活性级联聚合，并生产各种嵌段共聚物。

更新日期：2022-08-12

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