Reactivity of alpha-amino-peroxyl radicals and consequences for amine oxidation chemistry

Schuemperli, Martin T., Hammond, Ceri ORCID: https://orcid.org/0000-0002-9168-7674 and Hermans, Ive 2012. Reactivity of alpha-amino-peroxyl radicals and consequences for amine oxidation chemistry. Physical Chemistry Chemical Physics 14 (31) , pp. 11002-11007. 10.1039/C2CP41306J

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Abstract

A comparative theoretical study is presented on the formation and fate of α-amino-peroxyl radicals, recently proposed as important intermediates in the aerobic oxidation of amines. After radical abstraction of the weakly bonded αH-atom in the amine substrate, the α-amino-alkyl radical reacts irreversibly with O2, forming the corresponding α-amino-peroxyl radical. HO2˙-elimination from various types of α-amino-peroxyl radicals (forming the corresponding imine) and the kinetically competing substrate H-abstraction (forming the α-amino-hydroperoxide) were computationally characterized. Polar solvents were found to reduce the HO2˙-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.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Subjects:	Q Science > QD Chemistry
Publisher:	Royal Society of Chemistry
ISSN:	1463-9076
Last Modified:	25 Oct 2022 09:10
URI:	https://orca.cardiff.ac.uk/id/eprint/57538

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