Biochemistry and metabolic pathways of sulfenic acids and their derivatives

Broek, L. A. G. M. Van Den; Delbressine, L. P. C.; Ottenheijm, H. C. J.

doi:10.1002/9780470772287.ch16

Cited by 13 publications

(9 citation statements)

References 66 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Reaction of isolated (GS) 2 NHPt with sodium dithionite resulted in complete formation of GS-NH 2 Pt within 3 min as did ascorbate and GSH on prolonged incubation (1/2 and 2 h, respectively). These results are in agreement with a sulfenamide structure which is known to be cleaved under the above-mentioned reaction conditions (6, 31) liberating the corresponding amine and glutathione sulfenic acid that is assumed to decompose into GSO 2 H and GSSG (2,4,32).…”

Section: Resultssupporting

confidence: 86%

Additional Pathways of S-Conjugate Formation during Interaction of 4-Nitrosophenetole with Glutathione

Gallemann

Greif

Eyer

et al. 1998

Chem. Res. Toxicol.

View full text Add to dashboard Cite

The rapid reactions of nitrosoarenes with cellular SH groups have proved to be main metabolic conversions during detoxication. Interactions of the phenacetin metabolite 4-nitrosophenetole with glutathione have been investigated in detail during the last years, revealing a complex pattern of products depending on the stoichiometry of the reactants and reaction conditions. Eight metabolites have been identified hitherto, and the present work extends this medley by six additional products. Three metastable sulfenamides, 4-ethoxy-2,N-bis(glutathion-S-yl)-aniline, N4-(glutathion-S-yl)-4-amino-4'-ethoxydiphenylamine, and N-(glutathion-S-yl)-4-aminophenol, as well as the N-sulfenylquinonimine N-(glutathion-S-yl)-1,4-benzoquinonimine were characterized by chemical reactivity, chromatographic behavior, UV/vis absorption, 1H NMR, and FAB-MS data. The structure of the sulfenamide 2,N4-bis(glutathion-S-yl)-4-amino-4'-ethoxydiphenylamine could not be proved unequivocally, but is strongly suggested due to the chemical reactivity, chromatographic behavior, and UV/vis absorption of the compound. Finally, traces of 4-aminophenol were detected. A reaction scheme is presented explaining the formation of all identified metabolites via a central sulfenamide cation. Molecular orbital calculations for this sulfenamide cation have been performed, corroborating the proposed reaction mechanisms on the basis of Klopman's generalized perturbation theory.

show abstract

Section: Resultssupporting

confidence: 86%

Additional Pathways of S-Conjugate Formation during Interaction of 4-Nitrosophenetole with Glutathione

Gallemann

Greif

Eyer

et al. 1998

Chem. Res. Toxicol.

View full text Add to dashboard Cite

show abstract

“…Although it has been previously assumed that the one-electron couple between thiol and disulfide is the only redox chemistry of biological relevance, it has been recognized for more than 30 years that cysteine residues in proteins can be “overoxidized” beyond the disulfide form under conditions of oxidative stress . More recently, chemical and crystallographic evidence has been introduced for functional protein sulfenic acid moieties for native proteins, for example, nicotinamide adenine dinucleotide (reduced form) (NADH) peroxidase , NADH oxidase , nitrile hydratase , both classes of methionine sulfoxide reductases , and certain peroxiredoxins – . Furthermore, sulfenic acid derivatives have been implicated in the redox status regulation of certain cellular functions.…”

Section: Introductionmentioning

confidence: 99%

Reactive Sulfur Species: Kinetics and Mechanism of the Hydrolysis of Cysteine Thiosulfinate Ester

Ashby

2007

Chem. Res. Toxicol.

View full text Add to dashboard Cite

The kinetics and mechanisms of the hydrolysis of cysteine thiosulfinate ester (CyS(O)SCy ( x- ), x = 0-2) have been investigated by stopped-flow spectrophotometry between pH 6 and pH 14. The rate-limiting reaction of hydroxide is observed for pH < 13. More complicated kinetics are observed above pH 13, where the hydrolysis of CyS(O)SCy (2-) can be fast relative to subsequent reactions. The eventual products of hydrolysis are a 1:1 molar ratio of cystine (CySSCy) and cysteine sulfinic acid (CySO 2H) under all reaction conditions. The rate of hydrolysis is dependent upon the proton state of CyS(O)SCy ( x- ). Furthermore, cysteine thiosulfonate ester (CyS(O) 2SCy) was observed as an intermediate during the hydrolysis of CyS(O)SCy ( x- ) at lower pH. CyS(O) 2SCy eventually hydrolyzes to give stoichiometric amounts of CySSCy and CySO 2H. However, CySO 2H is observed under some conditions for which hydrolysis of CyS(O) 2SCy is relatively slow, thus suggesting multiple hydrolysis pathways for CyS(O)SCy ( x- ). The mechanism up to the rate-limiting step is proposed to be as follows: CyS(O)SCy (0) = H (+) + CyS(O)SCy (-), p K a3 = 7.32; CyS(O)SCy (-) = H (+) + CyS(O)SCy (2-), p K a4 = 7.92; CyS(O)SCy (0) + OH (-) --> products, P 0 k 0 = (5.0 +/- 0.01) x 10 (3) M (-1) s (-1); CyS(O)SCy (-) + OH (-) --> products, P 1 k 1 = 60 +/- 18 M (-1) s (-1); and CyS(O)SCy (2-) + OH (-) --> products, P 2 k 2 = 0.36 +/- 0.01 M (-1) s (-1), where P x is a constant (1

show abstract

“…Although the addition of sulfenic acids to unsaturated bonds has been chiefly used for demonstrating the existence of such unstable species as intermediates in organic and biological processes, , some intrinsic synthetic features justify the interest devoted to this reaction; for instance, it allows easy introduction of a sulfinyl group into a suitably unsaturated substrate. The addition of sulfenic acids to alkenes or alkynes is a concerted reaction in which the nature of the unsaturated bond, on one hand, and the structural features of the sulfenic acid, on the other, play a relevant role, the former on the regioselectivity and the latter on the total yield of the addition, since stabilizing effects of the sulfenic acid structure, such as high steric demands and/or intramolecular hydrogen bonding, could prevent its self-condensation to give thiosulfinate.…”

Section: Introductionmentioning

confidence: 99%

β-Sulfinyl α,β-Unsaturated Carbonyl Compounds from Enantiomerically Pure Sulfenic Acids

et al. 2001

View full text Add to dashboard Cite

The addition of enantiopure sulfenic acids to oxoalkynes constitutes a new and efficient methodology for the synthesis of beta-sulfinyl alpha,beta-unsaturated carbonyl compounds. Sulfenic acids 3 and 4 were generated by thermolysis of suitable precursors and trapped in situ by oxoalkynes 5, affording (R(S),E)- and (S(S),E)-3-alkylsulfinyl-1-phenyl-2-propen-1-ones, 4-alkylsulfinyl-3-buten-2-ones, and 3-[(1S)-isoborneol-10-sulfinyl]-2-propenoates 6 and 7 in good yields and in enantiomerically pure form after simple column chromatography. (R(S),E)-3-[(1S)-isoborneol-10-sulfinyl]-1-phenyl-2-propen-1-one (6(R)a) was involved as a heterodiene in inverse-electron-demanding Diels-Alder reactions with readily available electron-rich dienophiles 14 and 15, corroborating in each case the sulfinyl auxiliary capability in controlling the stereochemical outcome of these cycloadditions. Furthermore, the addition of methylmagnesium iodide to the carbonyl moiety of 6(R)a demonstrated that the chiral sulfur atom exerts a remote stereocontrol in this reaction if assisted by the hydroxy group being part of the isoborneol substituent.

show abstract

Biochemistry and metabolic pathways of sulfenic acids and their derivatives

Cited by 13 publications

References 66 publications

Additional Pathways of S-Conjugate Formation during Interaction of 4-Nitrosophenetole with Glutathione

Additional Pathways of S-Conjugate Formation during Interaction of 4-Nitrosophenetole with Glutathione

Reactive Sulfur Species: Kinetics and Mechanism of the Hydrolysis of Cysteine Thiosulfinate Ester

β-Sulfinyl α,β-Unsaturated Carbonyl Compounds from Enantiomerically Pure Sulfenic Acids

Contact Info

Product

Resources

About