Vitamin B12 Catalysis: Probing the Structure/Efficacy Relationship

Vitamin B12 is a cofactor for many enzymes, but it also functions as a catalyst in C−C bond‐forming reactions. Herein, the impact of corrin structural modifications on their catalytic efficacy was examined. Derivatives with various substituents at c‐, d‐, and meso‐positions were synthesised by using...

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Bibliographic Details
Published in:Chemistry : a European journal 2017-05, Vol.23 (29), p.7024-7030
Main Authors: Karczewski, Maksymilian, Ociepa, Michał, Pluta, Katarzyna, ó Proinsias, Keith, Gryko, Dorota
Format: Article
Language:English
Subjects:
Catalysis
Catalysts
diazo compounds
Effectiveness
homogeneous catalysis
natural products
structure–activity relationships
substituent effects
Vitamin B12
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Summary:Vitamin B12 is a cofactor for many enzymes, but it also functions as a catalyst in C−C bond‐forming reactions. Herein, the impact of corrin structural modifications on their catalytic efficacy was examined. Derivatives with various substituents at c‐, d‐, and meso‐positions were synthesised by using traditional and new microwave methodologies, and then tested in the model reaction of 1,1‐diphenylethylene with ethyl diazoacetate. To complement the experimental data, cyclic voltammetry and DFT calculations were performed. Mainly alterations at the c‐ or d‐positions influence both the reaction yield and selectivity. Maximum potential of vitamins: Derivatives of vitamin B12 modified at the c‐, d‐, and meso‐positions were synthesized by using new microwave methodology and tested as catalysts in the model reaction of 1,1‐diphenylethylene with ethyl diazoacetate. The results show that mainly alterations at the c‐ and d‐positions influenced the catalytic efficacy of vitamin B12 derivatives (see figure).
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201606059