Cobalt-catalyzed C–H cyanations: Insights into the reaction mechanism and the role of London dispersion

Beilstein Journal of Organic Chemistry

Eric Detmar¹  Martin Breugst¹  Valentin Müller²  Lutz Ackermann²  Daniel Zell² 

[1] Department für Chemie, Universität zu Köln, Greinstraße 4, 50939 Köln, Germany;Institut für Organische und Biomolekulare Chemie, Georg-August-Universität Göttingen, Tammannstraße 2, 37077 Göttingen, Germany;

关键词: catalysis;    C–H activation;    density functional theory;    London dispersion;    reaction mechanisms;   

DOI  :  10.3762/bjoc.14.130

来源: DOAJ

【 摘 要 】

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 functional theory and also experimentally. Based on our investigations, we propose a plausible reaction mechanism for this transformation that is in line with the experimental observations. Additional calculations, including NCIPLOT, dispersion interaction densities, and local energy decomposition analysis, for the model cyanation of 2-phenylpyridine furthermore highlight that London dispersion is an important factor that enables this challenging C–H transformation. Nonbonding interactions between the Cp* ligand and aromatic and C–H-rich fragments of other ligands at the cobalt center significantly contribute to a stabilization of cobalt intermediates and transition states.

【 授权许可】

Unknown