近日，南京大学谢劲团队报道了可交换氯原子转移自由基反应。这一研究成果于2026年10月28日发表在《自然》期刊上。

原子转移自由基反应，包括原子转移自由基加成（ATRA）与原子转移自由基聚合（ATRP），是合成功能化小分子与聚合物的一类通用方法。采用易得的非活化烷基氯替代活化有机卤化物，是该领域的前沿方向；该方向需要断裂底物中键能更高的 C–Cl 键，同时保留产物中键能更弱的 C–Cl 键。

研究组报道一种双铜接力催化策略以克服这一难点：双核铜配合物选择性活化非活化烷基氯中稳定性高的 C–Cl 键，单核铜催化剂则可控介导 C–Cl 键的重建。根据是否加入单核铜组分，反应路径可在 ATRA 型反应与 ATRP 型聚合之间切换，由此搭建可调控的氯原子转移自由基反应平台。该方法不仅能够合成结构多样的 ATRA 产物与 α 端基功能化聚丙烯酸酯，还可在温和条件下直接改性聚氯乙烯（PVC）。该工作证明了非活化有机氯化合物在有机合成与高分子科学中的有效应用。

附：英文原文

Title: Switchable Chlorine Atom Transfer Radical Reactions

Author: Huang, Jun, Liu, Yu, Yan, Wencheng, Dong, Guichao, Zhang, Xinyue, Chen, Hongliang, Zhao, Shiyi, Xu, Zhou, Zhu, Chengjian, Han, Jie, Xie, Jin

Issue&Volume: 2026-10-28

Abstract: Atom transfer radical reactions—encompassing atom transfer radical addition (ATRA)1 and atom transfer radical polymerization (ATRP)2—provide a versatile route to synthesize functionalized small molecules and polymers. Using readily available unactivated alkyl chlorides3 instead of activated organohalides represents the state-of-the-art in this field, as this requires cleaving stronger C–Cl bonds in the substrates while preserving weaker ones in the products. Here we describe a dual-copper relay catalytic strategy to overcome this limitation. A dinuclear copper complex selectively activates the robust C–Cl bond of unactivated alkyl chlorides, while a mononuclear copper catalyst mediates controllable C–Cl bond reconstruction. The reaction pathway can be switched between ATRA and ATRP-type reactions in the presence or absence of the mononuclear copper partner, thus providing a switchable platform for chlorine atom transfer radical reactions. This protocol can not only enable synthesis of structurally diverse ATRA products and α-end-functionalized polyacrylates, but allow for direct modification of poly(vinyl chloride) (PVC) under mild reaction conditions. It demonstrates the successful utility of unactivated organochlorides in organic synthesis and polymer science.

DOI: 10.1038/s41586-026-11348-z

Source:https://www.nature.com/articles/s41586-026-11348-z