title: Vitamin B12Catalysis: Probing the Structure/Efficacy Relationship.
abstract: Vitamin B12is 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.
authors.affiliation: Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224, Warsaw, Poland.
authors.forename: Maksymilian
authors.initials: M
authors.lastname: Karczewski
authors.affiliation: Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224, Warsaw, Poland.
authors.forename: Michał
authors.initials: M
authors.lastname: Ociepa
authors.affiliation: Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224, Warsaw, Poland.
authors.forename: Katarzyna
authors.initials: K
authors.lastname: Pluta
authors.affiliation: Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224, Warsaw, Poland.
authors.forename: Keith
authors.initials: K
authors.lastname: Ó Proinsias
authors.affiliation: Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224, Warsaw, Poland.
authors.forename: Dorota
authors.identifier: http://orcid.org/0000-0002-5197-4222
authors.initials: D
authors.lastname: Gryko
mesh_terms: D001688:Biological Products / Q000737:chemistry; D002384:Catalysis; D003979:Diazonium Compounds / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D013329:Structure-Activity Relationship; D014805:Vitamin B 12 / Q000737:chemistry*
chemical_list: D001688:Biological Products; D003979:Diazonium Compounds; C032111:diazoacetic ester; D014805:Vitamin B 12
keywords: diazo compounds; homogeneous catalysis; natural products; structure-activity relationships; substituent effects