title: Fe2+-catalyzed formation of nitriles and thionamides from intact glucosinolates.
abstract: The ratio of isothiocyanates to nitriles formed upon the hydrolysis of glucosinolates is a key factor determining the physiological effect of glucosinolate-containing plants and materials. A micellar electrokinetic capillary chromatography (MECC) method was used to study the nonenzymatic Fe2+-catalyzed transformation of glucosinolates. At room temperature, pH 5, and in the presence of only 2 molar excess of Fe2+ all glucosinolate was degraded in 24 h. At all molar excess Fe2+ tested, nitriles were the major compounds formed. Thionamides were also formed from glucosinolates that contained a side chain hydroxylated at C-2; in this case, trace amounts of oxazolidine-2-thione were also detected. The presence of Fe3+ had no effect. The nonenzymatic Fe2+-catalyzed transformation of glucosinolates involves the binding of Fe2+ to the glucosinolate to form a complex.
authors.affiliation: Department of Natural Sciences, Biochemistry and Natural Product Chemistry, Faculty of Life Sciences, University of Copenhagen, Frederiksberg, Denmark.
authors.forename: Natalia
authors.initials: N
authors.lastname: Bellostas
authors.forename: Anne D
authors.initials: AD
authors.lastname: Sørensen
authors.forename: Jens C
authors.initials: JC
authors.lastname: Sørensen
authors.forename: Hilmer
authors.initials: H
authors.lastname: Sørensen
mesh_terms: D000577:Amides / Q000138:chemical synthesis* / Q000737:chemistry; D001665:Binding Sites; D002384:Catalysis; D005961:Glucosinolates / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D006868:Hydrolysis; D007501:Iron / Q000737:chemistry*; D017879:Isothiocyanates / Q000737:chemistry*; D015394:Molecular Structure; D009570:Nitriles / Q000138:chemical synthesis* / Q000737:chemistry; D013997:Time Factors
chemical_list: D000577:Amides; D005961:Glucosinolates; D017879:Isothiocyanates; D009570:Nitriles; D007501:Iron