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Switchable Chlorine Atom Transfer Radical Reactions
Nature
(2026) Cite this article
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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.
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These authors contributed equally: Jun Huang, Yu Liu
State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, China
Jun Huang, Yu Liu, Wencheng Yan, Guichao Dong, Hongliang Chen, Shiyi Zhao, Chengjian Zhu, Jie Han & Jin Xie