The oxidation and reduction of sulphinic acids and their derivatives

Hoyle, Jeff

doi:10.1002/9780470772270.ch14

Cited by 5 publications

(3 citation statements)

References 132 publications

(6 reference statements)

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“…24 We have observed that under physiological conditions only small amounts of our peptide sulfinamides are converted to the corresponding sulfinic acids after 26 h. Because of the relatively longer half-life of sulfinic acid formation, the reduction of sulfinic acids to thiols is not considered to be a probable pathway. 52,53 This is supported by the fact that no significant sulfinic acid formation is observed in the presence of DTT.…”

Section: ■ Discussionmentioning

confidence: 83%

Reactivity of Nitroxyl-Derived Sulfinamides

Keceli

Toscano

2012

Biochemistry

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Sulfinamide [RS(O)NH(2)] formation is known to occur upon exposure of cysteine residues to nitroxyl (HNO), which has received recent attention as a potential heart failure therapeutic. Because this modification can alter protein structure and function, we have examined the reactivity of sulfinamides in several systems, including a small organic molecule, peptides, and a protein. Although it has generally been assumed that this thiol to sulfinamide modification is irreversible, we show that sulfinamides can be reduced back to the free thiol in the presence of excess thiol at physiological pH and temperature. We have examined this sulfinamide reduction both in peptides, where a cyclic intermediate analogous to that proposed for asparagine deamidation reactions potentially can contribute, and in a small organic molecule, where the mechanism is restricted to a direct thiolysis. These studies suggest that the contribution from the cyclic intermediate becomes more important in environments with lower dielectric constants. In addition, although sulfinic acid [RS(O)OH] formation is observed upon prolonged incubations in water, reduction of sulfinamides is found to dominate in the presence of thiols. Finally, studies with the cysteine protease, papain, suggest that the reduction of sulfinamide to the free thiol is viable in a protein environment.

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Section: ■ Discussionmentioning

confidence: 83%

Reactivity of Nitroxyl-Derived Sulfinamides

Keceli

Toscano

2012

Biochemistry

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“…Surprisingly, a major by-product of this reaction was the corresponding aryl sulfide 4a , which may arise from disproportionation of sulfonyl radicals to give thiols/thiolates or thiyl radicals ( Scheme 2B ). 17 , 18 Such species are known to engage in cross-coupling under Ni/photoredox conditions. 19 Higher temperatures appeared to increase sulfide formation and diminish overall conversion (entry 14).…”

Section: Introductionmentioning

confidence: 99%

Engaging sulfinate salts via Ni/photoredox dual catalysis enables facile C_sp2–SO₂R coupling

et al. 2018

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“…It is important to note that the proposed mechanism produces ionic and polar species already identified by other authors from the chemical reduction of sulfinic acids. 26 For NBS, it is proposed that an additional electrochemical step occurs involving an electron transfer through the nitro group, according to the following mechanism…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Reduction of Aromatic Sulfinic Acids in Dimethylsulfoxide

Angelo

Stradiotto

1997

J. Electrochem. Soc.

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The electrochemical reduction of benzenesulfinic, p-toluenesulfinic, and p-nitrobenzenesulfinic acids was studied in dimethylsulfoxide solutions. From cyclic voltammetry experiments, a chemical reaction following the first electron transfer was detected during the reduction process. A cyclic voltammetry technique using ultramicroelectrodes has provided kinetic parameters for the electron-transfer steps, from which it was possible to observe the influence of the ring substituent on the electrochemical reduction. The mechanism of the electroreduction of aromatic sulfinic acids in dimethylsulfoxide depends upon the nucleophilic attack of the radical anion produced on the starting compound during the reduction processes.

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The oxidation and reduction of sulphinic acids and their derivatives

Cited by 5 publications

References 132 publications

Reactivity of Nitroxyl-Derived Sulfinamides

Reactivity of Nitroxyl-Derived Sulfinamides

Engaging sulfinate salts via Ni/photoredox dual catalysis enables facile C_sp2–SO₂R coupling

Electrochemical Reduction of Aromatic Sulfinic Acids in Dimethylsulfoxide

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The oxidation and reduction of sulphinic acids and their derivatives

Cited by 5 publications

References 132 publications

Reactivity of Nitroxyl-Derived Sulfinamides

Reactivity of Nitroxyl-Derived Sulfinamides

Engaging sulfinate salts via Ni/photoredox dual catalysis enables facile Csp2–SO2R coupling

Electrochemical Reduction of Aromatic Sulfinic Acids in Dimethylsulfoxide

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Engaging sulfinate salts via Ni/photoredox dual catalysis enables facile C_sp2–SO₂R coupling