Pérez Ruíz, JorgeRamírez, Manuel R.Rentero, ChristianSessini, ValentinaMosquera, Marta E. G.Díaz Requejo, María MarPérez Romero, Pedro José2026-01-072026-01-072025-12-15Pérez‐Ruíz, J., Ramírez, M. R., Rentero, C., Sessini, V., Mosquera, M. E. G., Díaz‐Requejo, M. M., & Pérez, P. J. (2025). Functionalization of Polyolefins via Catalytic Nitrene Addition. Angewandte Chemie International Edition, 64(51), e22659. https://doi.org/10.1002/anie.202522659https://hdl.handle.net/10272/27601The post-polymerization functionalization of polyolefins has emerged as a key tool for obtaining new materials with enhanced properties. With an array of approaches being already reported, the incorporation of N-containing fragments en route to the generation of amino groups in yet scarce and not disclosed for the metal-catalyzed nitrene transfer strategy. Here we introduce such tactics employing silver-based catalysts for the incorporation of nitrene NTs (Ts = p-toluenesulfonyl) groups to commercially available polybutadienes. The process occurs at room temperature without appreciable chain scission or cross-linking processes and enables precise control of the degree of functionalization. Thermal analyses demonstrate a correlation between such degree and the Tg values of the functionalized polymers.engAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/Nitrene transfer • Polybutadiene amination • Polyolefin aziridination • Post-polymerization functionalization • Silver catalysisPolymersPolyolefinsPost-polymerizationjournal article10.1002/anie.202522659open access23 Química