Ionic-Liquid Hydrogen-Bonding Promoted Alcohols Amination over Cobalt Catalyst via Dihydrogen Autotransfer Mechanism.
ChemSusChem
; 16(17): e202300513, 2023 Sep 08.
Article
em En
| MEDLINE
| ID: mdl-37191041
ABSTRACT
Higher amines are important high-valuable chemicals with wide applications, and amination of alcohols is a green route to them, which however generally suffers from harsh reaction conditions and use of equivalent base. Herein, we report an ionic-liquid (IL) hydrogen-bonding promoted dihydrogen autotransfer strategy for amination of alcohols to higher amines over cobalt catalyst under base-free conditions. Co(BF4 )2 â
â
â
6 H2 O complexed with triphos and IL (e. g., tetrabutylphosphonium tetrafluoroborate, [P4444 ][BF4 ]) shows high performances for the reaction and is tolerant of a wide scope of amines and alcohols, affording higher amines in good to excellent yields. Mechanism investigation indicates that the [BF4 ]- anion activates the alcohol via hydrogen bonding, promoting transfer of both hydroxyl H and α-H atoms of alcohol to the cobalt catalyst to form an aldehyde intermediate and cobalt dihydride complex, which are involved in the subsequent reductive amination. This strategy provides a green and effective route for alcohol amination, which may have promising applications in alcohol-involved alkylation reactions.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
ChemSusChem
Assunto da revista:
QUIMICA
/
TOXICOLOGIA
Ano de publicação:
2023
Tipo de documento:
Article
País de afiliação:
China