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
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.
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BibTeX
@misc{kremser2026situ,
title = {{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}},
author = {Christoph Kremser and Dino Berthold and Alexander F. Siegle and Oliver Trapp},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15009720/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009720/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - 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
AU - Christoph Kremser
AU - Dino Berthold
AU - Alexander F. Siegle
AU - Oliver Trapp
PY - 2026
DA - 2026/10/01
PB - ChemRxiv
DO - 10.26434/chemrxiv.15009720/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009720/v1
AB - 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.
ER -