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Size-selective Catalytic Polymer Acylation with a Molecular Tetrahedron.
Chem ( IF 23.5 ) Pub Date : 2020-06-11 , DOI: 10.1016/j.chempr.2020.05.011
Mona Sharafi 1 , Kyle T McKay 1 , Monika Ivancic 1 , Dillon R McCarthy 1 , Natavan Dudkina 1 , Kyle E Murphy 1 , Sinu C Rajappan 1 , Joseph P Campbell 1 , Yuxiang Shen 2 , Appala Raju Badireddy 2 , Jianing Li 1 , Severin T Schneebeli 1, 3
Affiliation  

Selective catalysis at the molecular level represents a cornerstone of chemical synthesis. However, it still remains an open question how to elevate tunable catalysis to larger length scales to functionalize whole polymer chains in a selective manner. We now report a hydrazone-linked tetrahedron with wide openings, which acts as a catalyst to size-selectively functionalize polydisperse polymer mixtures. Our experimental and computational evidence supports a dual role of the hydrazone-linked tetrahedron. To accelerate functionalization of the polymer substrates, the tetrahedron (1) unfolds the polymer substrates and/or breaks the polymer aggregates and (2) enables target sites (amino groups) on the polymers to coordinate with catalytic units (triglyme) attached to the tetrahedron. With the tetrahedron as the catalyst, we find that the reactivity of the shorter polymers increases selectively. Our findings enable the possibility to engineer hydrolytically stable molecular polyhedra as organocatalysts for size-selective polymer modification.



中文翻译:

分子四面体的尺寸选择性催化聚合物酰化。

在分子水平上的选择性催化代表了化学合成的基石。然而,如何将可调节的催化作用提高到更大的长度规模以选择性地官能化整个聚合物链仍然是一个悬而未决的问题。现在,我们报告了一个具有宽开口的a连接的四面体,该四面体用作催化剂来选择性地官能化多分散聚合物混合物。我们的实验和计算证据支持了linked连接的四面体的双重作用。为了加速聚合物底物的功能化,四面体(1)展开聚合物底物和/或破坏聚合物聚集体,并且(2)使聚合物上的目标位点(氨基)能够与附着在四面体上的催化单元(三甘醇二甲醚)配合。以四面体为催化剂,我们发现较短的聚合物的反应性选择性地增加。我们的发现使我们有可能将水解稳定的分子多面体作为有机催化剂用于尺寸选择性聚合物改性。

更新日期:2020-06-11
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