Hydrogenobinamide and nibinamide-Metal-free ligand and Ni(II)-Analogue of the vitamin B1 2 precursor cobinamide

Christoph Kieninger, Evelyne Deery, Andrew D. Lawrence, Martin J. Warren, Bernhard Kräutler

Research output: Contribution to journalArticlepeer-review

Abstract

The replacement of cobalt in vitamin B12 derivatives by other transition metals is a formal path to non-natural corrins. Here, we describe nibinamide (Nibi), the novel Ni(II)-Analogue of the natural B12-derivative cobinamide (Cbi), and its synthesis from the metal-free ligand of Cbi, hydrogenobinamide (Hbi), both isolated as tetrafluoroborate salts. Aqueous solutions of the metal-free corrin Hbi are strongly fluorescent, whereas its Ni(II)-complex Nibi is non-luminescent. The solution structures of Hbi and of Nibi were characterized by hetero-nuclear NMR-spectroscopy. The Ni(II)-corrin Nibi was deduced to be roughly iso-structural to cob(I)inamide (CbiI) and to house a diamagnetic d8-metal-ioniso-electronic to CoI in CbiI. The chemically robust Nibi is, thus, a structural mimic of enzyme-Activated and reduced biosynthetic precursors of vitamin B12 and a B12-Antimetabolite potentially functioning as a specific inhibitor of B12-biosynthesis.

Original languageEnglish
Pages (from-to)627-633
Number of pages7
JournalJournal of Porphyrins and Phthalocyanines
Volume27
Issue number1-4
DOIs
Publication statusPublished - Jan 2023

Keywords

  • antivitamin B1 2
  • B1 2-Antimetabolite
  • corrin
  • tetrapyrrole
  • transition metal
  • vitamin B1 2

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