中国科学技术大学陈殿峰与上海交通大学朱峰团队宣布他们通过质子转移实现氮杂-π-烯丙基钯两性离子的区域扩散链生长聚合。相关论文于2025年12月1日发表于国际顶尖学术期刊《德国应用化学》杂志上。

该研究组报道了一个温和的钯催化的N-磺酰乙烯基亚氮醚的ROP通过π-烯丙基-pd^II-N^-两性离子中间体。这种聚合具有独特的引发和传播过程：1)质子从多种质子X─H/C─H键转移，以及2)随后的配体控制的区域发散烯丙基胺化反应。该方法通过扩大胺间距和增强官能团耐受性，超越了传统的碱促进聚合方法，可以合成一系列含氮的同源共聚物和共聚物。

据悉，质子转移是许多开环聚合（ROP）策略中的一个基本过程，可以在温和条件下精确控制聚合物链的生长。将质子转移机制与多功能反应中间体（如有机金属物质）相结合，为聚合物合成开辟新的化学空间提供了令人兴奋的机会。

附：英文原文

Title: Regiodivergent Chain-Growth Polymerization of Aza-π-Allylpalladium Zwitterions via Proton Transfer

Author: Yang-Yang Li, Bo Yang, Juan-Juan Han, Xuhui Liang, Shaoqiu Zheng, Feng Zhu, Dian-Feng Chen

Issue&Volume: 2025-12-01

Abstract: Proton transfer is a fundamental process in many ring-opening polymerization (ROP) strategies, imparting precise control over polymer chain growth under mild conditions. Merging proton transfer mechanism with versatile reactive intermediates—such as organometallic species—presents exciting opportunities to unlock new chemical space for polymer synthesis. Here, we report a mild palladium-catalyzed ROP of N-sulfonyl vinyl aziridines via a π-allyl-PdII-N zwitterionic intermediate. This polymerization features unique initiation and propagation proceeding through 1) proton transfer from a diversity of protic X─H/C─H bonds, and 2) subsequent ligand-controlled regiodivergent allylic amination reaction. This approach enables the synthesis of a range of nitrogen-containing homo- and copolymers, surpassing traditional base-promoted polymerization methods by expanding the amine spacing and enhancing functional group tolerance.

DOI: 10.1002/anie.202522529

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202522529