meso-Modified Cobalamins: Synthesis, Structure, and Properties

Aleksandra J Wierzba; Aleksandra Wincenciuk; Maksymilian Karczewski; Valentine I Vullev; Dorota Gryko

doi:10.1002/chem.201801807

meso-Modified Cobalamins: Synthesis, Structure, and Properties

Chemistry. 2018 Jul 20;24(41):10344-10356. doi: 10.1002/chem.201801807. Epub 2018 Jun 27.

Authors

Aleksandra J Wierzba¹, Aleksandra Wincenciuk^{1

2}, Maksymilian Karczewski¹, Valentine I Vullev³, Dorota Gryko¹

Affiliations

¹ Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224, Warsaw, Poland.
² Department of Chemistry, University of Warsaw, Pasteura 1, 02-093, Warsaw, Poland.
³ Bioengineering, Chemistry, Biochemistry, and Materials Science and Engineering, University of California, Riverside, Materials Science and Engineering Building, Room 235, Riverside, CA, 92521, USA.

PMID: 29719071
DOI: 10.1002/chem.201801807

Abstract

Vitamin B₁₂ and its derivatives present excellent paradigms for bioinspired catalysis. The inherent challenges for derivatizing cobalamins, such as vitamin B₁₂ , to incorporate them in supramolecular designs and materials, limit the range of their utility and applications. Herein, we present a synthetic approach toward derivatives of vitamin B₁₂ possessing electron-donating and -withdrawing substituents at the meso position (C10). Spectroscopic and cyclic voltammetry studies reveal that changes in the substitution pattern on the equatorial ligand have a significant impact on the electronic and optical properties of the cobalamin. These synthetic methods, therefore, provide invaluable routes not only for covalent linking to other structures, but also for attaining a wide range of functionalities for the derivatives of vitamin B₁₂ .

Keywords: cis-effect; cobalt; natural products; substituent effects; vitamin B12.