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| Home > Articles > Published articles > C-H Amination Reactions Mediated by Metastable Pseudo- O Masked Aryl-Co III -nitrene Species |
(Universitat de Girona. Departament de Química) (Universitat de Girona. Departament de Química) (ALBA Laboratori de Llum de Sincrotró) (Universitat Autònoma de Barcelona. Servei de Ressonància Magnètica Nuclear) (Universitat de Girona. Departament de Química) (Universitat de Girona. Departament de Química)
| Date: | 2022 |
| Abstract: | Cobalt-catalyzed C-H amination via M-nitrenoid species is spiking the interest of the research community. Understanding this process at a molecular level is a challenging task, and here we report a well-defined macrocyclic system featuring a pseudo- O aryl-Co III species that reacts with aliphatic azides to effect intramolecular C-N bond formation. Strikingly, a putative aryl-Co=NR nitrenoid intermediate species is formed and is rapidly trapped by a carboxylate ligand to form a carboxylate masked-nitrene, which functions as a shortcut to stabilize and guide the reaction to productive intramolecular C-N bond formation. On one hand, several intermediate species featuring the C-N bond formed have been isolated and structurally characterized, and the essential role of the carboxylate ligand has been proven. Complementarily, a thorough density functional theory study of the C-N bond formation mechanism explains at the molecular level the key role of the carboxylate-masked nitrene species, which is essential to tame the metastability of the putative aryl-Co III =NR nitrene species to effectively yield the C-N products. The solid molecular mechanistic scheme determined for the C-N bond forming reaction is fully supported by both experimental and computation complementary studies. |
| Grants: | Ministerio de Ciencia e Innovación CTQ2016-77989-P Agencia Estatal de Investigación PID2019-104498GB-I00 Agencia Estatal de Investigación PGC2018-098212-B-C22 Agencia Estatal de Investigación PGC2018-095808-B-I00 Agència de Gestió d'Ajuts Universitaris i de Recerca 2017/SGR-264 Agència de Gestió d'Ajuts Universitaris i de Recerca 2017/SGR-39 |
| Rights: | Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, fins i tot amb finalitats comercials, sempre i quan es reconegui l'autoria de l'obra original.  |
| Language: | Anglès |
| Document: | Article ; recerca ; Versió publicada |
| Published in: | Inorganic chemistry, Vol. 61, Issue 35 (August 2022) , p. 14075-14085, ISSN 1520-510X |
