The hydrogenobyric acid structure reveals the corrin ligand as an entatic state module empowering B12 cofactors for catalysis

Christoph Kieninger, Evelyne Deery, Andrew D. Lawrence, Maren Podewitz, Klaus Wurst, Emi Nemoto-Smith, Florian J. Widner, Joseph A. Baker, Steffen Jockusch, Christoph R. Kreutz, Klaus R. Liedl, Karl Gruber, Martin J. Warren, Bernhard Kräutler

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he 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 desymmetrized “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 analogues of B12.
Original languageEnglish
Pages (from-to)10756-10760
Number of pages5
JournalAngewandte Chemie-International Edition
Issue number31
Early online date22 May 2019
Publication statusPublished - 29 Jul 2019

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