A Nickel(II)-Containing Vitaminâ
B12 Derivative with a Cofactor-F430-type π-System.
Angew Chem Int Ed Engl
; 57(50): 16308-16312, 2018 12 10.
Article
em En
| MEDLINE
| ID: mdl-30352140
ABSTRACT
F430 is a unique enzymatic cofactor in the production and oxidation of methane by strictly anaerobic bacteria. The key enzyme methyl coenzymeâ
M reductase (MCR) contains a hydroporphinoid nickel complex with a characteristic absorption maximum at around 430â
nm in its active site. Herein, the three-step semisynthesis of a hybrid NiII -containing corrinoid that partly resembles F430 in its structural and spectroscopic features from vitaminâ
B12 is presented. A key step of the route is the simultaneous demetalation and ring closure reaction of a 5,6-secocobalamin to metal-free 5,6-dihydroxy-5,6-dihydrohydrogenobalamin with cobaltocene and KCN under reductive conditions. Studies on the coordination chemistry of the novel compound support an earlier hypothesis why nature carefully selected a corphin over a corrin ligand in F430 for challenging nickel-catalyzed biochemical reactions.
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Coleções:
01-internacional
Base de dados:
MEDLINE
Assunto principal:
Vitamina B 12
/
Complexo Vitamínico B
/
Níquel
Idioma:
En
Revista:
Angew Chem Int Ed Engl
Ano de publicação:
2018
Tipo de documento:
Article
País de afiliação:
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