Issue 9, 2012

Non-symmetrically substituted phenoxazinones from laccase-mediated oxidative cross-coupling of aminophenols: an experimental and theoretical insight

Abstract

Oxidative cross-coupling reactions of substituted o-aminophenols were catalyzed by a commercial laccase to produce non-symmetrically substituted phenoxazinones for the first time. Identification by 1H-, 13C- and 31P-NMR, and by HPLC-PDA and HPLC-MS/MS of exclusively two kinds of substituted phenoxazinones out of four potential heterocyclic frameworks was confirmed by a DFT study. The redox-properties of the substrates, their relative rates of conversion and the rigid docking of selected substrates led to a revisited mechanistic pathway for phenoxazinones biosynthesis. Our suggestions concern both the first formal two-electron oxidation by laccase and the first intermolecular 1,4-conjugated addition which secures the observed regioselectivity.

Graphical abstract: Non-symmetrically substituted phenoxazinones from laccase-mediated oxidative cross-coupling of aminophenols: an experimental and theoretical insight

Supplementary files

Article information

Article type
Paper
Submitted
20 May 2011
Accepted
03 Nov 2011
First published
18 Jan 2012

Org. Biomol. Chem., 2012,10, 1834-1846

Non-symmetrically substituted phenoxazinones from laccase-mediated oxidative cross-coupling of aminophenols: an experimental and theoretical insight

F. Bruyneel, G. Dive and J. Marchand-Brynaert, Org. Biomol. Chem., 2012, 10, 1834 DOI: 10.1039/C1OB05795B

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