Ligand design broadens NiI-catalysed C(sp2)–heteroatom couplings of aryl bromides at low catalyst loadings

article Ligand design broadens NiI-catalysed C(sp2)–heteroatom couplings of aryl bromides at low catalyst loadings epub_ahead yes Aleksander Bena author 4197c39e-e8ec-11ed-86cb-afed934cd664 Trisha Banik author 506b8e06-c59a-11ee-a1af-ae470719e7d3 Christos Giannoudis author 1bd506c6-e8ec-11ed-86cb-d495f63f2dcd Florian Ortis author e34c9177-3208-11ee-ac71-a6a15cf2ef290000-0002-0458-5187 Daniel Bím author Haralds Baunis author 2eea55ec-e8ec-11ed-86cb-d9c76787acfe Gayathri Palissery author b02c9d47-50c9-11ef-b52e-b2180bf00ccd Bartholomäus Pieber author 93e5e5b2-0da6-11ed-8a41-af589a0247260000-0001-8689-388X BaPi department GradSch department RaKl department Photoactive ligands for transformative nickel catalysis project IST-BRIDGE: International postdoctoral program project The formation of C(sp2)–heteroatom bonds through cross-coupling catalysis is central to the synthesis of pharmaceuticals, agrochemicals and materials. Whereas Pd0/PdII catalysis requires substrate-specific ligand optimization to balance the competing demands of oxidative addition and reductive elimination, NiI/NiIII catalysis offers a complementary strategy because the bond-forming step is intrinsically favourable. However, contemporary NiI/NiIII methodologies suffer from insufficient oxidative addition reactivity, restricting the aryl halide scope and requiring high catalyst loadings. Here we show that mechanistically guided ligand design overcomes these limitations. Together with a non-nucleophilic base additive that promotes direct visible-light generation of NiI from a bench-stable NiII precatalyst, this ligand design enables the coupling of electron-rich aryl bromides with N-, O-, S- and P-based nucleophiles at nickel loadings as low as 100 ppm. The method is compatible with sterically encumbered nucleophiles and enables gram-scale synthesis and late-stage functionalization of complex molecules. Springer Nature2026 eng Nature Catalysis 2520-115810.1038/s41929-026-01616-6 Bena A, Banik T, Giannoudis C, et al. Ligand design broadens NiI-catalysed C(sp2)–heteroatom couplings of aryl bromides at low catalyst loadings. Nature Catalysis. 2026. doi:<a href="https://doi.org/10.1038/s41929-026-01616-6">10.1038/s41929-026-01616-6</a> A. Bena, T. Banik, C. Giannoudis, F. Ortis, D. Bím, H. Baunis, G. Palissery, B. Pieber, Nature Catalysis (2026). Bena, A., Banik, T., Giannoudis, C., Ortis, F., Bím, D., Baunis, H., … Pieber, B. (2026). Ligand design broadens NiI-catalysed C(sp2)–heteroatom couplings of aryl bromides at low catalyst loadings. Nature Catalysis. Springer Nature. <a href="https://doi.org/10.1038/s41929-026-01616-6">https://doi.org/10.1038/s41929-026-01616-6</a> A. Bena et al., “Ligand design broadens NiI-catalysed C(sp2)–heteroatom couplings of aryl bromides at low catalyst loadings,” Nature Catalysis. Springer Nature, 2026. Bena A, Banik T, Giannoudis C, Ortis F, Bím D, Baunis H, Palissery G, Pieber B. 2026. Ligand design broadens NiI-catalysed C(sp2)–heteroatom couplings of aryl bromides at low catalyst loadings. Nature Catalysis. Bena, Aleksander, et al. “Ligand Design Broadens NiI-Catalysed C(Sp2)–Heteroatom Couplings of Aryl Bromides at Low Catalyst Loadings.” Nature Catalysis, Springer Nature, 2026, doi:<a href="https://doi.org/10.1038/s41929-026-01616-6">10.1038/s41929-026-01616-6</a>. Bena, Aleksander, Trisha Banik, Christos Giannoudis, Florian Ortis, Daniel Bím, Haralds Baunis, Gayathri Palissery, and Bartholomäus Pieber. “Ligand Design Broadens NiI-Catalysed C(Sp2)–Heteroatom Couplings of Aryl Bromides at Low Catalyst Loadings.” Nature Catalysis. Springer Nature, 2026. <a href="https://doi.org/10.1038/s41929-026-01616-6">https://doi.org/10.1038/s41929-026-01616-6</a>. 230942026-10-11T22:02:06Z2026-10-14T06:32:42Z