Fe2+-catalyzed formation of nitriles and thionamides from intact glucosinolates.
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.
Bellostas
Natalia
N
Department of Natural Sciences, Biochemistry and Natural Product Chemistry, Faculty of Life Sciences, University of Copenhagen, Frederiksberg, Denmark.
Sørensen
Anne D
AD
Sørensen
Jens C
JC
Sørensen
Hilmer
H
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
D000577:Amides; D005961:Glucosinolates; D017879:Isothiocyanates; D009570:Nitriles; D007501:Iron