74764-51-5Relevant articles and documents
Cobalt-catalyzed C–H cyanations: Insights into the reaction mechanism and the role of London dispersion
Detmar, Eric,Müller, Valentin,Zell, Daniel,Ackermann, Lutz,Breugst, Martin
, p. 1537 - 1545 (2018)
Carboxylate-assisted cobalt(III)-catalyzed C–H cyanations are highly efficient processes for the synthesis of (hetero)aromatic nitriles. We have now analyzed the cyanation of differently substituted 2-phenylpyridines in detail computationally by density f
Design of an Electron-Withdrawing Benzonitrile Ligand for Ni-Catalyzed Cross-Coupling Involving Tertiary Nucleophiles
Edjoc, Racquel K.,Mills, L. Reginald,Rousseaux, Sophie A. L.
supporting information, p. 10422 - 10428 (2021/07/26)
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.
Aminoalkyl radicals as halogen-atom transfer agents for activation of alkyl and aryl halides
Constantin, Timothée,Juliá, Fabio,Leonori, Daniele,Regni, Alessio,Sheikh, Nadeem S.,Zanini, Margherita
, p. 1021 - 1026 (2020/03/10)
Organic halides are important building blocks in synthesis, but their use in (photo)redox chemistry is limited by their low reduction potentials. Halogen-atom transfer remains the most reliable approach to exploit these substrates in radical processes despite its requirement for hazardous reagents and initiators such as tributyltin hydride. In this study, we demonstrate that a-aminoalkyl radicals, easily accessible from simple amines, promote the homolytic activation of carbon-halogen bonds with a reactivity profile mirroring that of classical tin radicals. This strategy conveniently engages alkyl and aryl halides in a wide range of redox transformations to construct sp3-sp3, sp3-sp2, and sp2-sp2 carbon-carbon bonds under mild conditions with high chemoselectivity.
