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., Liedl, Klaus R., Gruber, Karl, Warren, Martin J. and Kräutler, Bernhard (2019) The hydrogenobyric acid structure reveals the corrin ligand as an entatic state module empowering B12 cofactors for catalysis. Angewandte Chemie International Edition, 58 (31). pp. 10756-10760. ISSN 1433-7851

[img]
Preview
PDF (Published_Version) - Published Version
Available under License Creative Commons Attribution.

Download (2MB) | Preview

Abstract

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.

Item Type: Article
Faculty \ School: Faculty of Science
Related URLs:
Depositing User: LivePure Connector
Date Deposited: 28 Aug 2020 00:05
Last Modified: 22 Sep 2020 23:56
URI: https://ueaeprints.uea.ac.uk/id/eprint/76700
DOI: 10.1002/anie.201904713

Actions (login required)

View Item View Item