In situ Activation of Ni(II) with Boronic Acids and Application of a Phosphasilinane Ligand enable the Suzuki-Miyaura Cross-Coupling of Deactivated (Hetero)Aryl Chlorides
Year: 2026
Type: preprint
Abstract: The important substitution of costly palladium catalysts with earth-abundant nickel alternatives in Suzuki-Miyaura cross-coupling reactions is still problematic for challenging substrates, such as heteroaryls and (hetero)aryl chlorides. In this context, we report the application of low Vbur and electron-rich biaryl-based phosphasilinane ligands in nickel-catalyzed Suzuki-Miyaura cross-coupling reaction of electron-rich (hetero)aryl-chlorides with aryl boronic acid substrates, at catalyst loadings as low as 0.5 mol-% on gram-scale synthesis. To overcome the use of unstable Ni(0)-sources, the activation of cheap and bench-stable L2NiCl2 precatalysts with boronic acids was investigated and successfully applied, e.g., in the synthesis of intermediates for agrochemical and pharmaceutical products. Furthermore, this method enabled the synthesis of bench- and base-stable L2Ni(3-furyl)Cl complex, which was directly applied in cross-coupling reactions.
Source: ChemRxiv
Institution: Ludwig-Maximilians-Universität München
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W7215034097