Oxidation of thiols to sulphonic acids with Oxone®/NaHCO3 and KBrO3

Parida, Keshaba Nanda; Chandra, Ajeet; Moorthy, Jarugu Narasimha

doi:10.1002/slct.201600028

Cited by 21 publications

(22 citation statements)

References 42 publications

(16 reference statements)

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“…Regarding its use in the synthesis of organochalcogen compounds, Oxone® was used in the oxidation of sulfides to sulfoxides and sulfones, oxidation of thiols to sulfonic acids, oxyhalogenation of thiols and disulfides, oxidative coupling of thiols to disulfides, oxidation of selenides to selenones, and in the enantioselective oxidation of disulfides . Oxone® was used to prepare symmetric thiosulfonates, 3‐arylthio indoles, and 2‐aminobenzothiazoles …”

Section: Introductionmentioning

confidence: 99%

Selenomethoxylation of Alkenes Promoted by Oxone®

et al. 2018

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We describe herein an alternative method for the selenomethoxylation of unactivated alkenes using Oxone® as a stoichiometric oxidant. The electrophilic species of selenium were easily generated in situ by the reaction of diorganyl diselenides with Oxone®. By this efficient and simple approach, β‐methoxy‐selenides were obtained in moderate to excellent yields at room temperature in an open flask, starting from alkenes by using methanol as both nucleophile and solvent. When a mixture of H2O/CH3CN was employed as the solvent, β‐hydroxy‐selenides were selectively obtained under mild conditions.

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Section: Introductionmentioning

confidence: 99%

Selenomethoxylation of Alkenes Promoted by Oxone®

et al. 2018

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“…The incorporation of an additional boronic ester in 2Ox pair improves chemoselectivity by decreasing the amount of byproducts compared to 1Ox (Figure 2a). 27 Further analysis by LC-MS (Figure 2b) confirmed the formation of 1Ox and 2Ox,with The benefit of the pre-coordination on disulfide formation of BSC≃OSC (1Ox) and BSCSB≃OSCSO (2Ox) is the most pronounced at 2000 µM but it can be also seen at lower concentrations (200 and 20 µM). In case of 2Ox, only few side products have been formed most likely due to higher percentage of fraction bound compared to 1OX.…”

Section: Synthesis Of Dynamic Covalent Peptide Tagsmentioning

confidence: 80%

Dual stimuli-responsive dynamic covalent peptide tags: Towards sequence-controlled release in tumor-like microenvironments

Zegota

Müller

Lantzberg

et al. 2021

Preprint

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Dynamic covalent chemistry (DCvC) has emerged as a versatile synthetic tool for devising stable, stimuli-responsive bioconjugates. The interplay of binding affinity, association and dissociation constants exhibits a strong influence on the selectivity of the reaction, the conversion rate, as well as the stability in aqueous solutions. Nevertheless, dynamic covalent interactions often exhibit fast binding in combination with fast dissociation events and vice versa. To overcome the intrinsic limitation, we have designed dynamic covalent peptide tags combining two different pairs of dynamic covalent interactions with different reaction kinetics:(1) the fast association of boronic acid and catechol that forms pH-sensitive and rapidly dissociating boronate esters, and (2) the slower formation of a redox-active disulfide bond with slow dissociation rate. Pre-coordination of the thiols of the cysteine residues by the fast boronic acid-catechol interaction primarily yields the heterodimers proving selectivity and self-sorting capability of the reaction, with improved complex stability in aqueous solution and even in the acidic tumor-like extracellular microenvironment. The resulting bis-peptide conjugate responds to pH changes within the physiological range as well as to a redox environment that is similar to certain conditions found inside cancer cells. We believe that such tags hold great promise, through cooperative effects, for controlling the stability of bioconjugates under dilution in aqueous media, as well as designing intelligent pharmaceutics that react to distinct biological stimuli in cellular environments.

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“…The sulfoxides 2(O) – 4(O) and sulfones 2(O 2 ) – 4(O 2 ) , produced by oxidation of the sulfides, were analyzed by LC–HRMS (Table ) to verify that their MS characteristics were consistent with the proposed S -oxidation products. All three DON-thiols were readily oxidized to their corresponding sulfoxides and sulfones using Oxone in a one-step reaction . The oxidation to the sulfoxides was virtually instantaneous, while oxidation to the sulfones was complete within ca.…”

Section: Resultsmentioning

confidence: 99%

“…All three DON-thiols were readily oxidized to their corresponding sulfoxides and sulfones using Oxone in a one-step reaction. 16 The oxidation to the sulfoxides was virtually instantaneous, while oxidation to the sulfones was complete within ca. 6 h for 3 and 4, whereas 2 was oxidized to a ca.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Oxidative Release of Thiol-Conjugated Forms of the Mycotoxin 4-Deoxynivalenol

Uhlig

Ivanova

Miles

2019

Chem. Res. Toxicol.

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Deoxynivalenol (DON) is a trichothecene mycotoxin that is produced by several species of Fusarium, which may infect grain crops. DON, as well as other type-B trichothecenes, contain an α,β-unsaturated carbonyl group that may react with sulfhydryl groups in, for example, amino acids and peptides. Such conjugates have been shown to occur in plants. Nucleophilic addition of thiols to the conjugated double bond in DON afforded several isomeric reaction products, and the thermodynamically favored isomers of DON-10-cysteine and DON-10-glutathione have been prepared and characterized previously. This study reports the preparation and characterization of the kinetically favored DON-10cysteine isomer. We subsequently studied and compared the rate of the deconjugation reaction of the two DON-10-cysteine isomers and the thermodynamically favored DON-10-glutathione adduct. The deconjugation rate of the thermodynamically favored thiol conjugates was slow with half-lives of weeks even at pH 10.7, while the kinetically favored DON-10-cysteine isomer deconjugated within a few hours, affording free DON. We adapted a simple and rapid oxidation protocol in which the sulfide linkage was oxidized to a sulfoxide or sulfone that, when treated with the base, rapidly eliminated the adducted thiol as its sulfenate or sulfinate to afford free DON. The deconjugation reactions of the sulfoxides and sulfones of thermodynamically favored DON-10-thiols were complete within hours or minutes at pH 10.7, respectively. The increase in deconjugation rates for the kinetically favored DON-10-cysteine were less dramatic. Oxidation of sulfides to sulfoxides is known to occur in vivo, and thus, our data show that thiol-conjugated DON might become bioavailable via sulfide oxidation followed by elimination to regenerate DON. The oxidation−elimination approach could also be useful for the indirect quantification of DON-10-thiol conjugates in plant and animal tissues.

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Oxidation of thiols to sulphonic acids with Oxone^®/NaHCO₃ and KBrO₃

Cited by 21 publications

References 42 publications

Selenomethoxylation of Alkenes Promoted by Oxone®

Selenomethoxylation of Alkenes Promoted by Oxone®

Dual stimuli-responsive dynamic covalent peptide tags: Towards sequence-controlled release in tumor-like microenvironments

Oxidative Release of Thiol-Conjugated Forms of the Mycotoxin 4-Deoxynivalenol

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