Journal article
Reactivity of α-amino-peroxyl radicals and consequences for amine oxidation chemistry.
- Schümperli MT ETH Zurich, Department of Chemistry and Applied Bio-Sciences, Wolfgang-Pauli-Strasse 10, 8093 Zurich, Switzerland.
- Hammond C
- Hermans I
- 2012-07-11
Published in:
- Physical chemistry chemical physics : PCCP. - 2012
English
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 O(2), forming the corresponding α-amino-peroxyl radical. HO(2)˙-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 HO(2)˙-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.
- Language
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- English
- Open access status
- closed
- Identifiers
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- DOI 10.1039/c2cp41306j
- PMID 22777062
- Persistent URL
- https://sonar.ch/global/documents/51913
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