| Title: |
C-H Amination Reactions Mediated by Metastable Pseudo- O Masked Aryl-Co III -nitrene Species |
| Authors: |
Capdevila, Lorena; Montilla, Marc; Planas, Oriol; Brotons, Artur; Salvador, Pedro; Martin-Diaconescu, Vlad; Parella Coll, Teodor; Luis, Josep M.; Ribas, Xavi |
| Publication Year: |
2022 |
| Collection: |
Universitat Autònoma de Barcelona: Dipòsit Digital de Documents de la UAB |
| Description: |
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. |
| Document Type: |
article in journal/newspaper |
| File Description: |
application/pdf |
| Language: |
English |
| ISSN: |
1520510X |
| Relation: |
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; Inorganic chemistry; Vol. 61, Issue 35 (August 2022), p. 14075-14085; https://ddd.uab.cat/record/265343; urn:10.1021/acs.inorgchem.2c02111; urn:oai:ddd.uab.cat:265343; urn:pmcid:PMC9455280; urn:pmid:35997604; urn:oai:pubmedcentral.nih.gov:9455280; urn:articleid:1520510Xv61n35p14075; urn:scopus_id:85137164226 |
| Availability: |
https://ddd.uab.cat/record/265343 |
| Rights: |
open access ; 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. ; https://creativecommons.org/licenses/by/4.0/ |
| Accession Number: |
edsbas.8709F68C |
| Database: |
BASE |