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A Nickel(II)-Containing Vitamin B12 Derivative with a Cofactor-F430-type π-System


Brenig, Christopher; Prieto, Lucas; Oetterli, René; Zelder, Felix (2018). A Nickel(II)-Containing Vitamin B12 Derivative with a Cofactor-F430-type π-System. Angewandte Chemie Internationale Edition, 57(50):16308-16312.

Abstract

F430 is a unique enzymatic cofactor in the production and oxidation of methane by strictly anaerobic bacteria. The key enzyme methyl coenzyme M reductase (MCR) contains a hydroporphinoid nickel complex with a characteristic absorption maximum at around 430 nm in its active site. Herein, the three‐step semisynthesis of a hybrid NiII‐containing corrinoid that partly resembles F430 in its structural and spectroscopic features from vitamin B12 is presented. A key step of the route is the simultaneous demetalation and ring closure reaction of a 5,6‐secocobalamin to metal‐free 5,6‐dihydroxy‐5,6‐dihydrohydrogenobalamin with cobaltocene and KCN under reductive conditions. Studies on the coordination chemistry of the novel compound support an earlier hypothesis why nature carefully selected a corphin over a corrin ligand in F430 for challenging nickel‐catalyzed biochemical reactions.

Abstract

F430 is a unique enzymatic cofactor in the production and oxidation of methane by strictly anaerobic bacteria. The key enzyme methyl coenzyme M reductase (MCR) contains a hydroporphinoid nickel complex with a characteristic absorption maximum at around 430 nm in its active site. Herein, the three‐step semisynthesis of a hybrid NiII‐containing corrinoid that partly resembles F430 in its structural and spectroscopic features from vitamin B12 is presented. A key step of the route is the simultaneous demetalation and ring closure reaction of a 5,6‐secocobalamin to metal‐free 5,6‐dihydroxy‐5,6‐dihydrohydrogenobalamin with cobaltocene and KCN under reductive conditions. Studies on the coordination chemistry of the novel compound support an earlier hypothesis why nature carefully selected a corphin over a corrin ligand in F430 for challenging nickel‐catalyzed biochemical reactions.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > Catalysis
Physical Sciences > General Chemistry
Language:English
Date:10 December 2018
Deposited On:13 Feb 2020 13:20
Last Modified:22 Jun 2024 01:41
Publisher:Wiley-VCH Verlag
ISSN:1433-7851
OA Status:Green
Publisher DOI:https://doi.org/10.1002/anie.201810983
Project Information:
  • : FunderUZH
  • : Grant IDFK‐17‐088
  • : Project TitleForschungskredit
  • Content: Accepted Version