Solvent- and metal-free selective oxidation of thiols to disulfides using I2/DMSO catalytic system

Bettanin, Luana; Saba, Sumbal; Galetto, Fábio Z.; Mike, Gustavo A.; Rafique, Jamal; Braga, Antônio L.

doi:10.1016/j.tetlet.2017.11.009

Cited by 47 publications

(14 citation statements)

References 36 publications

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“…This compound was synthesized according to a modification of a previously reported procedure (Scheme S4). 20 4-Aminothiophenol 6a (200 mg, 1.60 mmol, 1 equiv.) was dissolved in a minimal amount of MeOH (2 mL) and DMSO (60 μL) and treated with I 2 (162 mg, 0.64 mmol, 0.4 equiv.).…”

Section: Methodsmentioning

confidence: 99%

Chemoselective Cyclopropanation over Carbene Y–H Insertion Catalyzed by an Engineered Carbene Transferase

et al. 2018

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Hemoproteins have recently emerged as promising biocatalysts for promoting a variety of carbene transfer reactions including cyclopropanation and Y-H insertion (Y = N, S, Si, B). For these and synthetic carbene transfer catalysts alike, achieving high chemoselectivity toward cyclopropanation in olefin substrates bearing unprotected Y-H groups has proven remarkably challenging due to competition from the more facile carbene Y-H insertion reaction. In this report, we describe the development of a novel artificial metalloenzyme based on an engineered myoglobin incorporating a serine-ligated Co-porphyrin cofactor that is capable of offering high selectivity toward olefin cyclopropanation over N-H and Si-H insertion. Intramolecular competition experiments revealed a distinct and dramatically altered chemoselectivity of the Mb(H64V,V68A,H93S)[Co(ppIX)] variant in carbene transfer reactions compared to myoglobin-based variants containing the native histidine-ligated heme cofactor or other metal/proximal ligand substitutions. These studies highlight the functional plasticity of myoglobin as a "carbene transferase" and illustrate how modulation of the cofactor environment within this metalloprotein scaffold represents a valuable strategy for accessing carbene transfer reactivity not exhibited by naturally occurring hemoproteins or transition metal catalysts.

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Section: Methodsmentioning

confidence: 99%

Chemoselective Cyclopropanation over Carbene Y–H Insertion Catalyzed by an Engineered Carbene Transferase

et al. 2018

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“…Coincidently, DMSO has been used in the oxidation of HI that affords iodine and water (Scheme 2, eq 3). [34][35][36][37][38] Similarly, the analogous sulfonium chloride and bromide were proposed as intermediates in the oxidative dissolution of silver in DMSO-HX systems. 39 Since water would deplete the ether cleaving agent and lead to sidereactions, it seemed unsuitable to use DMSO as the acid scavenger in aluminum triiodide-mediated ether cleavages.…”

Section: Syn Thesismentioning

confidence: 99%

Cleavage of Catechol Monoalkyl Ethers by Aluminum Triiodide–Dimethyl Sulfoxide

Sang

Tian²,

Tu³

et al. 2018

Synthesis

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Using eugenol and vanillin as model substrates, a practical method is developed for the cleavage o-hydroxyphenyl alkyl ethers. Aluminum oxide iodide (O=AlI), generated in situ from aluminum triiodide and dimethyl sulfoxide, is the reactive ether cleaving species. The method is applicable to catechol monoalkyl ethers as well as normal phenyl alkyl ethers for the removal of methyl, ethyl, isopropyl, and benzyl groups. A variety of functional groups such as alkenyl, allyl, amide, cyano, formyl, keto, nitro, and halogen are well tolerated under the optimum conditions. Partial hydrodebromination was observed during the demethylation of 4-bromoguaiacol, and was resolved using excess DMSO as an acid scavenger. This convenient and efficient procedure would be a practical tool for the preparation of catechols.

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“…Unfortunately, in spite of these useful applications, aiming the production of these derivatives through the oxidation of cysteine remains synthetic challenge because of the numerous feasible reaction pathways and possible side products [ 16 , 17 ]. It has been shown that transformations of cysteine and cysteine-related molecules towards various products can be achieved via the development of catalytic reaction systems and/or exploiting the interlayer gallery of layered materials are needed [ 18 , 19 , 20 , 21 , 22 ].…”

Section: Introductionmentioning

confidence: 99%

Oxidation of Cysteinate Anions Immobilized in the Interlamellar Space of CaAl-Layered Double Hydroxide

et al. 2021

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L-Cysteinate-intercalated CaAl-layered double hydroxide (LDH) was prepared by the co-precipitation method producing highly crystalline hydrocalumite phase with a well-pillared interlayer gallery. The obtained materials were characterized by X-ray diffractometry, IR as well as Raman spectroscopies. By performing interlamellar oxidation reactions with peracetic acid as oxidant, oxidation of cysteinate to cystinate in aqueous and cysteinate sulfenic acid in acetonic suspensions occurred. The oxidations could be performed under mild conditions, at room temperature, under neutral pH and in air. It has been shown that the transformation pathways are due to the presence of the layered structure, that is, the confined space of the LDH behaved as molecular reactor.

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Solvent- and metal-free selective oxidation of thiols to disulfides using I2/DMSO catalytic system

Cited by 47 publications

References 36 publications

Chemoselective Cyclopropanation over Carbene Y–H Insertion Catalyzed by an Engineered Carbene Transferase

Chemoselective Cyclopropanation over Carbene Y–H Insertion Catalyzed by an Engineered Carbene Transferase

Cleavage of Catechol Monoalkyl Ethers by Aluminum Triiodide–Dimethyl Sulfoxide

Oxidation of Cysteinate Anions Immobilized in the Interlamellar Space of CaAl-Layered Double Hydroxide

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