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The Hydrogenobyric Acid Structure Reveals the Corrin Ligand as an Entatic State Module Empowering B12‐Cofactors for Catalysis

Kieninger, Christoph, Deery, Evelyne, Lawrence, Andrew D., Podewitz, Maren, Wurst, Klaus, Nemoto-Smith, Emi, Widner, Florian J., Baker, Joseph A., Jockusch, Steffen, Kreutz, Christoph R., and others. (2019) The Hydrogenobyric Acid Structure Reveals the Corrin Ligand as an Entatic State Module Empowering B12‐Cofactors for Catalysis. Angewandte Chemie, 58 (31). pp. 10756-10760. ISSN 0044-8249. (doi:10.1002/anie.201904713) (KAR id:74131)

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The B12 cofactors instill a natural curiosity regarding the primordial selection and evolution of their corrin ligand. Surprisingly, this important natural macrocycle has evaded molecular scrutiny, and its specific role in predisposing the incarcerated cobalt-ion for organometallic catalysis has remained obscure. Herein, we report the biosynthesis of the cobalt-free B12 corrin moiety, hydrogenobyric acid (Hby), a compound crafted through pathway redesign. Detailed insights from single crystal X-ray and solution structures of Hby have revealed a distorted helical cavity, redefining the pattern for binding cobalt-ions. Consequently, the corrin ligand coordinates cobalt-ions in de-symmetrized ‘entatic’ states, thereby promoting the activation

of B12-cofactors for their challenging chemical transitions. The availability of Hby also provides a route to the synthesis of transition metal analogs of B12.

Item Type: Article
DOI/Identification number: 10.1002/anie.201904713
Uncontrolled keywords: Cobalamins, Cobalt, Synthetic Biology, Vitamin, X-ray, structure
Subjects: Q Science > QD Chemistry
Divisions: Divisions > Division of Natural Sciences > School of Biosciences
Depositing User: Evelyne Deery
Date Deposited: 28 May 2019 09:15 UTC
Last Modified: 19 Feb 2021 14:21 UTC
Resource URI: (The current URI for this page, for reference purposes)
Deery, Evelyne:
Warren, Martin J.:
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