Structural basis of enzymatic benzene ring reduction - Archive ouverte HAL
Article Dans Une Revue Nature Chemical Biology Année : 2015

Structural basis of enzymatic benzene ring reduction

Tobias Weinert
  • Fonction : Auteur
Simona G. Huwiler
  • Fonction : Auteur
Johannes W. Kung
  • Fonction : Auteur
Sina Weidenweber
  • Fonction : Auteur
Petra Hellwig
Hans-Joachim Stärk
  • Fonction : Auteur
Till Biskup
  • Fonction : Auteur
Stefan Weber
  • Fonction : Auteur
Julien J. H. Cotelesage
  • Fonction : Auteur
Graham N. George
  • Fonction : Auteur
Ulrich Ermler
  • Fonction : Auteur
Matthias Boll
  • Fonction : Auteur

Résumé

In chemical synthesis, the widely used Birch reduction of aromatic compounds to cyclic dienes requires alkali metals in ammonia as extremely low-potential electron donors. An analogous reaction is catalyzed by benzoyl-coenzyme A reductases (BCRs) that have a key role in the globally important bacterial degradation of aromatic compounds at anoxic sites. Because of the lack of structural information, the catalytic mechanism of enzymatic benzene ring reduction remained obscure. Here, we present the structural characterization of a dearomatizing BCR containing an unprecedented tungsten cofactor that transfers electrons to the benzene ring in an aprotic cavity. Substrate binding induces proton transfer from the bulk solvent to the active site by expelling a Zn(2+) that is crucial for active site encapsulation. Our results shed light on the structural basis of an electron transfer process at the negative redox potential limit in biology. They open the door for biological or biomimetic alternatives to a basic chemical synthetic tool.
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Dates et versions

hal-03337406 , version 1 (07-09-2021)

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Citer

Tobias Weinert, Simona G. Huwiler, Johannes W. Kung, Sina Weidenweber, Petra Hellwig, et al.. Structural basis of enzymatic benzene ring reduction. Nature Chemical Biology, 2015, 11 (8), pp.586-591. ⟨10.1038/nchembio.1849⟩. ⟨hal-03337406⟩
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