Csp2–H Amination Reactions Mediated by Metastable Pseudo-Oh Masked Aryl-CoIII-nitrene Species
| Autor: | Lorena Capdevila, Marc Montilla, Oriol Planas, Artur Brotons, Pedro Salvador, Vlad Martin-Diaconescu, Teodor Parella, Josep M. Luis, Xavi Ribas |
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| Přispěvatelé: | Agencia Estatal de Investigación |
| Rok vydání: | 2022 |
| Předmět: | |
| Zdroj: | Inorganic Chemistry, 2022, vol. 61, núm. 35, p. 14075-14085 Articles publicats (D-Q) DUGiDocs – Universitat de Girona instname |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/acs.inorgchem.2c02111 |
| Popis: | 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-Oh aryl-CoIII species that reacts with aliphatic azides to effect intramolecular Csp2–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 Csp2–N bond formation. On one hand, several intermediate species featuring the Csp2–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 Csp2–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-CoIII═NR nitrene species to effectively yield the Csp2–N products. The solid molecular mechanistic scheme determined for the Csp2–N bond forming reaction is fully supported by both experimental and computation complementary studies This work was financially supported by MICINN (CTQ2016- 77989-P and PID2019-104498GB-I00 to X.R., PGC2018- 098212-B-C22 to J.M.L. and PGC2018-095808-B-I00 to T.P.) and Generalitat de Catalunya (2017SGR264 to X.R. and 2017SGR39 to J.M.L.) Open Access funding provided thanks to the CRUE-CSIC agreement with ACS |
| Databáze: | OpenAIRE |
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