A change in the mechanism of biomimetic oxidation of tertiary amines in response to appropriate structural features of the substrate, emerges from the investigation of the product pattern from N-benzylaziridine under bona fide radical or electron transfer conditions. This substrate is an amine endowed with a high oxidation potential as a result of steric constraint. Consequently, the hydrogen atom transfer route of oxidative N-dealkylation competes favorably with the electron transfer route, which is the mechanism observed for the reaction of conventional tertiary amines with metalloporphyrins and oxygen donors.
The oxidation of N-benzylaziridine induced by iron porphyrin: radical vs. electron transfer mechanism / Cuppoletti, A.; Dagostin, C.; Florea, C.; Galli, Carlo; Gentili, Patrizia; Lanzalunga, Osvaldo; Petride, A.; Petride, H.. - In: CHEMISTRY-A EUROPEAN JOURNAL. - ISSN 0947-6539. - 5:(1999), pp. 2993-2999. [10.1002/(SICI)1521-3765(19991001)5:10<2993::AID-CHEM2993>3.3.CO;2-3]
The oxidation of N-benzylaziridine induced by iron porphyrin: radical vs. electron transfer mechanism.
GALLI, Carlo;GENTILI, Patrizia;LANZALUNGA, Osvaldo;
1999
Abstract
A change in the mechanism of biomimetic oxidation of tertiary amines in response to appropriate structural features of the substrate, emerges from the investigation of the product pattern from N-benzylaziridine under bona fide radical or electron transfer conditions. This substrate is an amine endowed with a high oxidation potential as a result of steric constraint. Consequently, the hydrogen atom transfer route of oxidative N-dealkylation competes favorably with the electron transfer route, which is the mechanism observed for the reaction of conventional tertiary amines with metalloporphyrins and oxygen donors.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
