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

doi:10.1002/anie.201904713

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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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.

Original language	English
Pages (from-to)	10756-10760
Number of pages	5
Journal	Angewandte Chemie-International Edition
Volume	58
Issue number	31
Early online date	22 May 2019
DOIs	https://doi.org/10.1002/anie.201904713
Publication status	Published - 29 Jul 2019

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Martin Warren
- Martin.Warrenuea.acuk
- Faculty of Science - Group Leader
- Norwich Institute for Healthy Aging - Member
Person: Research Centre Member, Academic, Teaching & Research

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Kieninger, C., Deery, E., Lawrence, A. D., Podewitz, M., Wurst, K., Nemoto-Smith, E., Widner, F. J., Baker, J. A., Jockusch, S., Kreutz, C. R., Liedl, K. R., Gruber, K., Warren, M. J., & Kräutler, B. (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), 10756-10760. https://doi.org/10.1002/anie.201904713

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

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.",

author = "Christoph Kieninger and Evelyne Deery and Lawrence, {Andrew D.} and Maren Podewitz and Klaus Wurst and Emi Nemoto-Smith and Widner, {Florian J.} and Baker, {Joseph A.} and Steffen Jockusch and Kreutz, {Christoph R.} and Liedl, {Klaus R.} and Karl Gruber and Warren, {Martin J.} and Bernhard Kr{\"a}utler",

year = "2019",

month = jul,

day = "29",

doi = "10.1002/anie.201904713",

language = "English",

volume = "58",

pages = "10756--10760",

journal = "Angewandte Chemie-International Edition",

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Kieninger, C, Deery, E, Lawrence, AD, Podewitz, M, Wurst, K, Nemoto-Smith, E, Widner, FJ, Baker, JA, Jockusch, S, Kreutz, CR, Liedl, KR, Gruber, K, Warren, MJ & Kräutler, B 2019, 'The hydrogenobyric acid structure reveals the corrin ligand as an entatic state module empowering B₁₂ cofactors for catalysis', Angewandte Chemie-International Edition, vol. 58, no. 31, pp. 10756-10760. https://doi.org/10.1002/anie.201904713

TY - JOUR

T1 - The hydrogenobyric acid structure reveals the corrin ligand as an entatic state module empowering B12 cofactors for catalysis

AU - Kieninger, Christoph

AU - Deery, Evelyne

AU - Lawrence, Andrew D.

AU - Podewitz, Maren

AU - Wurst, Klaus

AU - Nemoto-Smith, Emi

AU - Widner, Florian J.

AU - Baker, Joseph A.

AU - Jockusch, Steffen

AU - Kreutz, Christoph R.

AU - Liedl, Klaus R.

AU - Gruber, Karl

AU - Warren, Martin J.

AU - Kräutler, Bernhard

PY - 2019/7/29

Y1 - 2019/7/29

N2 - 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.

AB - 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.

U2 - 10.1002/anie.201904713

DO - 10.1002/anie.201904713

M3 - Article

VL - 58

SP - 10756

EP - 10760

JO - Angewandte Chemie-International Edition

JF - Angewandte Chemie-International Edition

SN - 1433-7851

IS - 31

ER -

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

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