Recent advances in the application of CuAAC for the covalent immobilization of homogeneous catalysts, a decade of progress

The immobilization of homogeneous catalysts has become a central strategy in the design of efficient and sustainable catalytic systems. By anchoring well-defined molecular catalysts onto soluble or insoluble supports, it is possible to combine the high activity and selectivity of homogeneous catalysis with the operational benefits of heterogeneous systems, including ease of recovery, recyclability, and implementation within continuous flow processes. Among the various approaches to covalent immobilization, the copper-catalyzed azide-alkyne cycloaddition (CuAAC) stands out as a particularly versatile and reliable method. This “click” reaction offers exceptional robustness, functional group tolerance, and modularity, allowing for the immobilization of a broad range of catalytic species — organic and organometallic — under mild conditions. In this article, we update our review published in 2014 and highlight recent advances in the use of CuAAC for catalyst immobilization, from simple single-site catalysts to elaborate multicatalytic systems, including organometallic, organic and multifunctional catalysts, and photocatalysts. We also discuss how the triazole linkage itself can serve not only as a passive tether but also as a functional component, influencing the microenvironment and coordination behavior of the resulting materials. Despite its many strengths, CuAAC is not without limitations, such as the requirement for copper catalyst and potential interference of the triazole unit. These drawbacks are considered in the context of emerging complementary “click” immobilization strategies. Overall, CuAAC remains a cornerstone technology in the immobilization toolbox, offering a powerful platform for building next-generation supported catalysts that approach the performance of their homogeneous counterparts while enabling scalable and sustainable chemical processes.

Affiliations

UCLouvainSST/IMCN - Institute of Condensed Matter and Nanosciences

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Fernandes, A., Riant, O., & Jonas, A. (2025). Recent advances in the application of CuAAC for the covalent immobilization of homogeneous catalysts, a decade of progress. Tetrahedron, 192, 135108. https://doi.org/10.1016/j.tet.2025.135108 (Original work published 2025)