title: Designing the Molybdopterin Core through Regioselective Coupling of Building Blocks.
abstract: Molybdopterin is an essential cofactor for all forms of life. The cofactor is composed of a pterin moiety appended to a dithiolene-functionalized pyran ring, and through the dithiolene moiety it binds metal ions. Different synthetic strategies for dithiolene-functionalized pyran precursors that have been designed and synthesized are discussed. These precursors also harbor 1,2-diketone or osone functionality that has been condensed with 1,2-diaminobenzene or other heterocycles resulting in several quinoxaline or pterin derivatives. Use of additives improves the regioselectivity of the complexes. The molecules have been characterized by (1)H and (13)C NMR and IR spectroscopies, as well as by mass spectrometry. In addition, several compounds have been crystallographically characterized. The geometries of the synthesized molecules are more planar than the geometry of the cofactor found in proteins.
authors.affiliation: Department of Chemistry and Biochemistry, Duquesne University, 600 Forbes Ave, Pittsburgh, PA 15282 (USA).
authors.forename: Igor V
authors.initials: IV
authors.lastname: Pimkov
authors.affiliation: Department of Chemistry and Biochemistry, Duquesne University, 600 Forbes Ave, Pittsburgh, PA 15282 (USA).
authors.forename: Barbara
authors.initials: B
authors.lastname: Serli-Mitasev
authors.affiliation: Department of Chemistry and Biochemistry, Duquesne University, 600 Forbes Ave, Pittsburgh, PA 15282 (USA).
authors.forename: Antoinette A
authors.initials: AA
authors.lastname: Peterson
authors.affiliation: Department of Chemistry and Biochemistry, Duquesne University, 600 Forbes Ave, Pittsburgh, PA 15282 (USA).
authors.forename: Stephen C
authors.initials: SC
authors.lastname: Ratvasky
authors.affiliation: Department of Chemistry and Biochemistry, Duquesne University, 600 Forbes Ave, Pittsburgh, PA 15282 (USA).
authors.forename: Bernd
authors.initials: B
authors.lastname: Hammann
authors.affiliation: Department of Chemistry and Biochemistry, Duquesne University, 600 Forbes Ave, Pittsburgh, PA 15282 (USA). basu@duq.edu.
authors.forename: Partha
authors.initials: P
authors.lastname: Basu
mesh_terms: D013058:Mass Spectrometry; D015394:Molecular Structure; D008982:Molybdenum / Q000737:chemistry*; D010655:Phenylenediamines / Q000737:chemistry*; D011622:Pterins / Q000138:chemical synthesis* / Q000737:chemistry*
chemical_list: D010655:Phenylenediamines; D011622:Pterins; D008982:Molybdenum; C034193:1,2-diaminobenzene
keywords: bioinorganic chemistry; heterocyclic compounds; natural products; organic ligands; synthetic methods