1 research outputs found
Nondirected, Cu-Catalyzed sp<sup>3</sup> C–H Aminations with Hydroxylamine-Based Amination Reagents: Catalytic and Mechanistic Studies
This
work demonstrates the use of hydroxylamine-based amination
reagents RSO<sub>2</sub>NH-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-CH<sub>2</sub>(NTsOAc) as a major intermediate.
Stoichiometric reactivity of Ph-CH<sub>2</sub>(NTsOAc) to produce
Ph-CH<sub>2</sub>-NHTs suggests a two-cycle, radical pathway for C–H
amination, in which the decomposition of the employed diimine ligands
plays an important role