The authors acknowledge synthetic and spectroscopic support by Ursula Cornelissen, Stephanie Pehlke, Marianne Karbstein, Dr. Gerhardt Peters, and Madleen Sallmann.
Benzylic Ligand Hydroxylation Starting from a Dicopper μ-η2:η2 Peroxo Intermediate: Dramatic Acceleration of the Reaction by Hydrogen-Atom Donors†
Article first published online: 17 JUN 2011
Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Angewandte Chemie International Edition
Volume 50, Issue 30, pages 6924–6927, July 18, 2011
How to Cite
Rolff, M., Hamann, J. N. and Tuczek, F. (2011), Benzylic Ligand Hydroxylation Starting from a Dicopper μ-η2:η2 Peroxo Intermediate: Dramatic Acceleration of the Reaction by Hydrogen-Atom Donors. Angew. Chem. Int. Ed., 50: 6924–6927. doi: 10.1002/anie.201102332
- Issue published online: 13 JUL 2011
- Article first published online: 17 JUN 2011
- Manuscript Received: 4 APR 2011
- bioinorganic chemistry;
- type 2 monooxygenases;
- type 3 copper proteins;
Radicals in directed pathways: The μ-η2:η2 peroxo CuII2 intermediate 1 shows a much faster benzylic ligand hydroxylation than systems without phenol. This novel reactivity can be further accelerated by addition of external H-atom donors such as TEMPO-H. The results imply initial H-atom transfer leading to the formation of phenoxyl radicals. A highly reactive copper oxyl intermediate is then formed, which inserts oxygen into the benzylic CH bond.