Organic Chemistry

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

Authors

Abstract

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.

Content

Thumbnail image of Rousseaux-BenzonitrileLigand-Manuscript.pdf

Supplementary material

Thumbnail image of Rousseaux-BenzonitrileLigand-SI.pdf
Rousseaux-BenzonitrileLigand-SI
Thumbnail image of Rousseaux-BenzonitrileLigand-SI NMR.pdf
Rousseaux-BenzonitrileLigand-SI NMR