DFT Study on Mechanism of Ni-Al Bimetallic-Catalyzed C-H Cyclization to Construct Tricyclic Imidazoles: Roles of NHC Ligand and AlMe3.
J Org Chem
; 89(3): 1505-1514, 2024 Feb 02.
Article
de En
| MEDLINE
| ID: mdl-38217504
ABSTRACT
The mechanism of the Ni-Al bimetallic-catalyzed C-H cyclization to construct tricyclic imidazoles is investigated using density functional theory calculations. The calculation result shows that the reaction mechanism involves sequential steps of substrate coordination, ligand-to-ligand hydrogen transfer (LLHT), and C-C reductive elimination to produce the final product tricyclic imidazole. The LLHT step is calculated to be the rate-determining step. The oxidative addition of the benzimidazole C-H bond to the Ni center and the insertion of the alkene into the Ni-H bond occur concertedly in the LLHT step. The effects of N-heterocyclic carbene (NHC) ligands and AlMe3 on the reactivity and regioselectivity were also analyzed. These calculation results shed light on some ambiguous suggestions from experiments.
Texte intégral:
1
Collection:
01-internacional
Base de données:
MEDLINE
Langue:
En
Journal:
J Org Chem
/
J. org. chem
/
Journal of organic chemistry
Année:
2024
Type de document:
Article
Pays de publication:
États-Unis d'Amérique