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Redox-Neutral Syntheses and Electrochemical Studies of 10-Bromo-Substituted Light-Stable Antivitamin B12 Candidates


Brenig, Christopher; Mosberger, Leila; Baumann, Katja; Blacque, Olivier; Zelder, Felix (2021). Redox-Neutral Syntheses and Electrochemical Studies of 10-Bromo-Substituted Light-Stable Antivitamin B12 Candidates. Helvetica Chimica Acta, 104:e21000.

Abstract

This publication describes the straightforward and redox-neutral synthesis of 10-bromophenylethynylcobalamin and its facile conversion to 10-bromoaquacobalamin. In this approach, the phenylethynyl ligand acts as convenient light-stable protecting group that is removed in quantitative yield under acidic conditions. The proteolytic cleavage at pH 2.0 was studied under pseudo-first-order conditions and is 1.5 times slower than that of phenylethynylcobalamin with a hydrogen instead of a bromine at C(10). Preliminary electrochemical studies of organometallic ethynyl-Cbls (Cbl=cobalamin) are reported for the first time. A reduction potential urn:x-wiley:0018019X:media:hlca202100067:hlca202100067-math-0001 of −0.94 V vs. Ag/AgCl was determined for the CoIII/CoI reduction of 10-bromophenylethynylcobalamin. The positive potential shift of 180 mV compared to phenylethynylcobalamin is in agreement with earlier electrochemical studies of related cyanocobalamins.

Abstract

This publication describes the straightforward and redox-neutral synthesis of 10-bromophenylethynylcobalamin and its facile conversion to 10-bromoaquacobalamin. In this approach, the phenylethynyl ligand acts as convenient light-stable protecting group that is removed in quantitative yield under acidic conditions. The proteolytic cleavage at pH 2.0 was studied under pseudo-first-order conditions and is 1.5 times slower than that of phenylethynylcobalamin with a hydrogen instead of a bromine at C(10). Preliminary electrochemical studies of organometallic ethynyl-Cbls (Cbl=cobalamin) are reported for the first time. A reduction potential urn:x-wiley:0018019X:media:hlca202100067:hlca202100067-math-0001 of −0.94 V vs. Ag/AgCl was determined for the CoIII/CoI reduction of 10-bromophenylethynylcobalamin. The positive potential shift of 180 mV compared to phenylethynylcobalamin is in agreement with earlier electrochemical studies of related cyanocobalamins.

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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
Life Sciences > Biochemistry
Life Sciences > Drug Discovery
Physical Sciences > Physical and Theoretical Chemistry
Physical Sciences > Organic Chemistry
Physical Sciences > Inorganic Chemistry
Uncontrolled Keywords:Inorganic Chemistry, Organic Chemistry, Physical and Theoretical Chemistry, Drug Discovery, Biochemistry, Catalysis
Language:English
Date:1 August 2021
Deposited On:13 Jan 2022 14:42
Last Modified:26 Feb 2024 02:42
Publisher:Wiley Open Access
ISSN:1522-2675
OA Status:Hybrid
Free access at:Publisher DOI. An embargo period may apply.
Publisher DOI:https://doi.org/10.1002/hlca.202100067
  • Content: Published Version
  • Licence: Creative Commons: Attribution 4.0 International (CC BY 4.0)