Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 14, Issue 31, Pages 11002-11007Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c2cp41306j
Keywords
-
Funding
- ETH Zurich [17 09-3]
Ask authors/readers for more resources
A comparative theoretical study is presented on the formation and fate of alpha-amino-peroxyl radicals, recently proposed as important intermediates in the aerobic oxidation of amines. After radical abstraction of the weakly bonded alpha H-atom in the amine substrate, the alpha-amino-alkyl radical reacts irreversibly with O-2, forming the corresponding alpha-amino-peroxyl radical. HO2 center dot-elimination from various types of alpha-amino-peroxyl radicals (forming the corresponding imine) and the kinetically competing substrate H-abstraction (forming the alpha-amino-hydroperoxide) were computationally characterized. Polar solvents were found to reduce the HO2 center dot-elimination barrier, but increase the barrier for H-abstraction. Depending on the reaction conditions (gas or liquid phase, amine concentration, nature of the solvent, and temperature), either of the two mechanisms is favored. The consequences for aerobic amine oxidation chemistry are discussed.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available