Summary
A Nature study reports a dual-copper strategy for using unactivated alkyl chlorides in chlorine atom-transfer radical chemistry. The approach can switch between small-molecule synthesis and polymer reactions.
A research article published in Nature on 28 October 2026 reports a dual-copper strategy for chlorine atom-transfer radical reactions using unactivated alkyl chlorides. The method assigns bond activation and bond reconstruction to different copper complexes, allowing the reaction pathway to switch between small-molecule synthesis and polymer chemistry.
How the copper relay works
Atom-transfer radical addition (ATRA) uses radical intermediates to add new groups to molecules. Atom-transfer radical polymerization (ATRP) uses atom transfer to regulate radical activity as polymer chains grow. Both depend on breaking and reforming bonds involving halogen atoms.
Unactivated alkyl chlorides are attractive starting materials, but their carbon–chlorine (C–Cl) bonds are difficult to break. The challenge described in the paper is to activate a robust C–Cl bond in the starting material while preserving weaker C–Cl bonds that may be present in the products.
The researchers report a relay involving two forms of copper catalyst. A dinuclear copper complex—one containing two copper atoms—selectively activates the C–Cl bond in an unactivated alkyl chloride. A mononuclear copper catalyst, containing one copper atom, mediates controlled reconstruction of C–Cl bonds. The reaction can be directed towards ATRA or ATRP-type chemistry by including or omitting the mononuclear copper partner.
Uses in molecules and polymers
The reported method supports the synthesis of structurally diverse ATRA products and α-end-functionalized polyacrylates, polymers with a functional group at one end of the chain. The paper also reports direct modification of poly(vinyl chloride), or PVC, under mild reaction conditions.
The significance is that unactivated organochlorides can serve as inputs to multiple kinds of radical transformation, rather than being limited to reactions that rely on more activated organohalides. The switchable catalyst arrangement links small-molecule functionalization and polymer modification through a shared chlorine-transfer approach.
The work is reported as peer-reviewed, accepted research in Nature. Its abstract describes the reaction strategy and the classes of products and polymers made; it does not provide numerical yields or detailed reaction conditions.