Nondirected, Cu-Catalyzed sp3 C-H Aminations with Hydroxylamine-Based Amination Reagents: Catalytic and Mechanistic Studies.
Organometallics
; 36(7): 1259-1268, 2017 Apr 10.
Article
de En
| MEDLINE
| ID: mdl-31223182
ABSTRACT
This work demonstrates the use of hydroxylamine-based amination reagents RSO2NH-OAc for the nondirected, Cu-catalyzed amination of benzylic C-H bonds. The amination reagents can be prepared on a gram scale, are benchtop stable, and provide benzylic C-H amination products with up to 86% yield. Mechanistic studies of the established reactivity with toluene as substrate reveal a ligand-promoted, Cu-catalyzed mechanism proceeding through Ph-CH2(NTsOAc) as a major intermediate. Stoichiometric reactivity of Ph-CH2(NTsOAc) to produce Ph-CH2-NHTs suggests a two-cycle, radical pathway for C-H amination, in which the decomposition of the employed diimine ligands plays an important role.
Texte intégral:
1
Collection:
01-internacional
Base de données:
MEDLINE
Langue:
En
Journal:
Organometallics
Année:
2017
Type de document:
Article
Pays d'affiliation:
États-Unis d'Amérique