Mechanistic snapshots of rhodium-catalyzed acylnitrene transfer reactions.
Science
; 381(6657): 525-532, 2023 Aug 04.
Article
em En
| MEDLINE
| ID: mdl-37471480
ABSTRACT
Rhodium (Rh) acylnitrene complexes are widely implicated in catalytic C-H amidation reactions but have eluded isolation and structural characterization. To overcome this challenge, we designed a chromophoric octahedral Rh complex with a bidentate dioxazolone ligand, in which photoinduced metal-to-ligand charge transfer initiates catalytic C-H amidation. X-ray photocrystallographic analysis of the Rh-dioxazolone complex allowed structural elucidation of the targeted Rh-acylnitrenoid and provided firm evidence that the singlet nitrenoid species is primarily responsible for acylamino transfer reactions. We also monitored in crystallo reaction of a nucleophile with the in situ-generated Rh-acylnitrenoid, which provided a crystallographically traceable reaction system to capture mechanistic snapshots of nitrenoid transfer.
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Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Ano de publicação:
2023
Tipo de documento:
Article