DFT Study of Mechanism and Stereochemistry of Nickel-Catalyzed trans-Arylative Desymmetrizing Cyclization of Alkyne-Tethered Malononitriles.
J Org Chem
; 87(23): 16079-16083, 2022 12 02.
Article
em En
| MEDLINE
| ID: mdl-36383065
ABSTRACT
Present here is a density functional theory (DFT) study of the mechanism and origin of enantioselectivity of Ni-catalyzed desymmetric cyclization of alkyne-tethered malononitriles and aryl boronic acids. The reaction starts from transmetalation and arylnickel addition, followed by trans to cis isomerization to give cis-alkenyl nickel species. The stereodetermining step is the CN insertion, which prefers a transition state with the bystander CN group staying away from the ligand to reduce steric repulsion, and gives the final (R)-product.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Assunto principal:
Alcinos
/
Níquel
Idioma:
En
Revista:
J Org Chem
Ano de publicação:
2022
Tipo de documento:
Article
País de afiliação:
China