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Design of an Electron-Withdrawing Benzonitrile Ligand for Ni-Catalyzed Cross-Coupling Involving Tertiary Nucleophiles

preprint
submitted on 25.03.2021, 01:01 and posted on 29.03.2021, 07:25 by Reginald Mills, Racquel Edjoc, Sophie Rousseaux
The design of new ligands for cross-coupling is essential for developing new catalytic reactions that access valuable products such as pharmaceuticals. In this report, we exploit the reactivity of nitrile-containing additives in Ni catalysis to design a benzonitrile-containing ligand for cross-coupling involving tertiary nucleophiles. Kinetic and Hammett studies are used to elucidate the role of the optimized ligand, which demonstrate that the benzonitrile moiety acts as an electron-acceptor to promote reductive elimination over β­-hydride elimination, and stabilize low-valent Ni. With these conditions, a protocol for decyanation–metalation and Ni-catalyzed arylation is conducted, enabling access to quaternary α-arylnitriles from disubstituted malononitriles.

Funding

Canada Foundation for Innovation - 19119, 35261

Canada Research Chair - 950-230935

Ministry of Research and Innovation

Natural Sciences and Engineering Research Council of Canada

University of Toronto

History

Email Address of Submitting Author

sophie.rousseaux@utoronto.ca

Institution

University of Toronto

Country

Canada

ORCID For Submitting Author

0000-0002-6505-5593

Declaration of Conflict of Interest

No conflict of interest

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