Supramolecular Chemistry Group, Centre of Macromolecular Chemistry (CMaC), Department of Organic and Macromolecular Chemistry, Ghent University, Krijgslaan 281 S4, 9000, Ghent, Belgium.
Present address: Innovation Center of NanoMedicine, Kawasaki Institute of Industrial Promotion, 3-25-14, Tonomachi, Kawasaki-ku, Kawasaki, 210-0821, Japan.
Angew Chem Int Ed Engl. 2022 Jul 18;61(29):e202201781. doi: 10.1002/anie.202201781. Epub 2022 May 25.
The catalytic conversion of esters to amides represents new opportunities in the synthetic diversification and upcycling of polymers, as esters are commonly featured in various polymer structures. Yet, direct amidation is typically hampered by poor reaction kinetics and the effects of polymer structure on the reactivity remain poorly understood. We report the accelerated amidation for amines with additional hydrogen bond donating or accepting groups. These amines facilitate the expeditious (co)amidation of polymers with pendant ester groups, displaying at least a 400-fold higher reactivity relative to polyesters with esters in the main chain. Furthermore, a positive correlation between the reactivity and degree of polymerization for poly(methyl acrylate) suggests a hydrogen-bond mediated intramolecular activation of the esters, which was confirmed by FT-IR spectroscopy and basic molecular mechanics modeling. The reported method paves the way to synthesize diverse (co)polymers with amide side chains from readily available polymeric precursors.
酯到酰胺的催化转化为聚合物的合成多样化和升级提供了新的机会，因为酯通常存在于各种聚合物结构中。然而，直接酰胺化通常受到反应动力学差的限制，并且聚合物结构对反应性的影响仍了解甚少。我们报告了具有额外氢键供体或受体基团的胺的加速酰胺化。这些胺促进了带有侧基酯的聚合物的快速（共）酰胺化，与主链中带有酯的聚酯相比，反应性至少提高了 400 倍。此外，聚（甲基丙烯酸甲酯）的反应性和聚合度之间的正相关关系表明酯的氢键介导的分子内活化，这通过傅里叶变换红外光谱和基本分子力学模型得到了证实。所报道的方法为从现成的聚合物前体合成具有酰胺侧链的各种（共）聚合物铺平了道路。
