Author
Listed:
- Jonathan Fuchs
(University of Freiburg)
- Unai Fernández-Arévalo
(Centro de Investigaciones Biológicas Margarita Salas-CSIC)
- Ulrike Demmer
(Max Planck Institute of Biophysics)
- Eduardo Díaz
(Centro de Investigaciones Biológicas Margarita Salas-CSIC)
- G. Matthias Ullmann
(University of Bayreuth)
- Antonio J. Pierik
(RPTU Kaiserslautern-Landau)
- Ulrich Ermler
(Max Planck Institute of Biophysics)
- Matthias Boll
(University of Freiburg)
Abstract
The alkali metal- and ammonia-dependent Birch reduction is the classical synthetic method for achieving dihydro additions to arenes, typically yielding 1,4-cyclodienes. A mild biological alternative to this process are 1,5-dienoyl-coenzyme A (CoA)-forming class I and II benzoyl-CoA reductases (BCRs), widely abundant key enzymes in the biodegradation of aromatic compounds at anoxic environments. To obtain a comprehensive mechanistic understanding of class I BCR catalysis, we produced the active site subunits from a denitrifying bacterium and determined the X-ray structure of its substrate and product complexes at 1.4 Å revealing non-canonical double-cubane [8Fe-9S] and active site aqua-[4Fe-4S] clusters. Together with kinetic, spectroscopic and QM/MM studies, we provide evidence for a radical mechanism with a [4Fe-4S] cluster-bound water molecule acting as hydrogen atom and electron donor at potentials beyond the biological redox window. An analogous Birch-like radical mechanism is applied by class II BCRs with the catalytic water bound to a tungsten-bis-metallopterin cofactor. The use of activated, metal-bound water ligands as hydrogen atom donor serves as a basic blueprint for future enzymatic or biomimetic Birch reduction processes.
Suggested Citation
Jonathan Fuchs & Unai Fernández-Arévalo & Ulrike Demmer & Eduardo Díaz & G. Matthias Ullmann & Antonio J. Pierik & Ulrich Ermler & Matthias Boll, 2025.
"Enzymatic Birch reduction via hydrogen atom transfer at [4Fe-4S]-OH2 and [8Fe-9S] clusters,"
Nature Communications, Nature, vol. 16(1), pages 1-11, December.
Handle:
RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-58418-w
DOI: 10.1038/s41467-025-58418-w
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