25373-49-3Relevant articles and documents
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.
Cu(0)@Al2O3/SiO2 NPs: An efficient reusable catalyst for the cross coupling reactions of aryl chlorides with amines and anilines
Reddy, P. Linga,Arundhathi,Rawat, Diwan S.
, p. 92121 - 92127 (2015/11/17)
The C-N cross coupling reaction of aryl chlorides with various alkyl/aryl amines catalyzed by copper nanoparticles impregnated on alumina/silica support (Cu(0)@Al2O3/SiO2) was investigated. The prepared catalyst was characterized for its intrinsic physico-chemical and textural properties using XRD, XPS, HR-TEM, BET surface area, SEM-EDAX, H2-TPR and ICP-AES techniques. The catalyst exhibits excellent reactivity and efficacy in the cross-coupling of a wide range of alkyl/aryl amines including challenging anilines with aryl chlorides. The catalyst offers significant advantages such as brevity, milder reaction conditions, excellent yields and high functional group tolerance for C-N cross coupling when compared with the other reported methods. Moreover, this atom-economical methodology does not require an additional ligand or co-catalyst/activator. The Cu(0)@Al2O3/SiO2 catalyst was efficiently applied to a gram scale synthesis of 7-chloro-4-(4-(2-nitrophenyl)piperazin-1-yl)quinolone (2k). The robustness of the catalyst was examined by reusing it for five consecutive runs.
Mild transition-metal-free amination of fluoroarenes catalyzed by fluoride ions
Dehe, Daniel,Munstein, Isabel,Reis, Andreas,Thiel, Werner R.
experimental part, p. 1151 - 1154 (2011/05/02)
Trimethylsilyl-protected heterocycles undergo N-C bond formation with a variety of electron-deficient fluoroarenes catalyzed by fluoride ions. This reaction avoids stoichiometric amounts of base and thus makes N-arylheterocycles accessible in a very mild and transition-metal-free way.
