C_sp2-H Amination Reactions Mediated by Metastable Pseudo-O_h Masked Aryl-Co^III-nitrene Species.

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_h aryl-Co^III species that reacts with aliphatic azides to effect intramolecular C_sp2-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_sp2-N bond formation. On one hand, several intermediate species featuring the C_sp2-N bond formed have been isolated and st

SUBMITTER: Capdevila L 

PROVIDER: S-EPMC9455280 | biostudies-literature | 2022 Sep

REPOSITORIES: biostudies-literature