Bis(<i>p</i>-methoxyphenyl) Selenoxide as a Mild and Selective Oxidizing Agent

OguraFumio,; YamaguchiHachiro,; OtsuboTetsuo,; TanakaHiroyuki,

doi:10.1246/bcsj.55.641

Cited by 38 publications

(7 citation statements)

References 6 publications

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“…3a-(Phenylthio)cholestane (29). 3/3-Chlorocholest-4-ene (1.07 g, 2.63 mmol) was hydrogenated in 30 mL of ether in the presence of 100 mg of 10% Pd/C under positive pressure (hydrogen balloon).…”

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Desulfurization with nickel and cobalt boride: scope, selectivity, stereochemistry, and deuterium-labeling studies

Back¹,

Baron²,

Yang³

1993

J. Org. Chem.

115

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Section: Methodsmentioning

confidence: 99%

“…Of 3a-(PhenyIthio)cholestane (29). Compound 29 (44 mg, 0.090 mmol) was desulfurized via the general method, using sodium borodeuteride and anhydrous NiCl2 in a 3:1 mixture of CH3OD and THF.…”

Section: Methodsmentioning

confidence: 99%

Desulfurization with nickel and cobalt boride: scope, selectivity, stereochemistry, and deuterium-labeling studies

Back¹,

Baron²,

Yang³

1993

J. Org. Chem.

115

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“…What follows next is regeneration of the antioxidant. Reduction of selenoxide to selenide is a facile process and mild reducing agents such as thiols, ascorbate and phosphines are known to bring about such transformations. Reduction of phenoxyl radicals to phenols by the same reducing agents has less precedence in the literature.…”

Section: Resultsmentioning

confidence: 99%

“…At this point, the reactive peroxyl radicalh as been reduced to form an alcohol and ap henoxyl radical/selenoxide-a process which is likelyt ob et hermodynamically favoured.W hat follows next is regenerationo ft he antioxidant. Reduction of selenoxide to selenide is afacile process and mild reducing agents such as thiols, [25] ascorbate [26] and phosphines [27] are known to bring about such transformations.R eductiono fp henoxyl radicals to phenols by the same reducing Table 3. Inhibited rates of peroxidation (R inh )a nd inhibition times (T inh ) for antioxidant 9 with NAC as aco-antioxidanta tpH2,5and 7. agents has less precedence in the literature.W es peculate that one-electron reduction across an aqueous-lipid interphase is occurring.…”

Section: Mechanistic Considerationsmentioning

confidence: 99%

Chain‐Breaking Phenolic 2,3‐Dihydrobenzo[b]selenophene Antioxidants: Proximity Effects and Regeneration Studies

Singh

Yan

Poon

et al. 2017

Chemistry A European J

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Phenolic 2,3-dihydrobenzo[b]selenophene antioxidants bearing an OH-group ortho (9), meta (10, 11) and para (8) to the Se were prepared by seleno-Claisen rearrangement/intramolecular hydroselenation. meta-Isomer (11) was studied by X-ray crystallography. The radical-trapping activity and regenerability of compounds 8-11 were evaluated using a two-phase system in which linoleic acid was undergoing peroxidation in the lipid phase while regeneration of the antioxidant by co-antioxidants (N-acetylcysteine, glutathione, dithiothreitol, ascorbic acid, tris(carboxyethyl)phosphine hydrochloride) was ongoing in the aqueous layer. Compound 9 quenched peroxyl radicals more efficiently than α-tocopherol. It also provided the most long-lasting antioxidant protection. With thiol co-antioxidants it could inhibit peroxidation for more than five-fold longer than the natural product. Regeneration was more efficient when the aqueous phase pH was slightly acidic. Since calculated O-H bond dissociation energies for 8-11 were substantially larger than for α-tocopherol, an antioxidant mechanism involving O-atom transfer from peroxyl to selenium was proposed. The resulting phenolic selenoxide/alkoxyl radical would then exchange a hydrogen atom in a solvent cage before antioxidant regeneration at the aqueous lipid interphase.

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“…Since the 60s, sulfoxides are well known for their capacity of acting as mild oxidizing agents [1]. Selenoxides can engage in a similar, but faster, redox chemistry, and can easily oxidize thiols to disulfides at room temperature [2][3][4][5] (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

The Key Role of Chalcogenurane Intermediates in the Reduction Mechanism of Sulfoxides and Selenoxides by Thiols Explored In Silico

Madabeni

Orian

2023

IJMS

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Sulfoxides and selenoxides oxidize thiols to disulfides while being reduced back to sulfides and selenides. While the reduction mechanism of sulfoxides to sulfides has been thoroughly explored experimentally as well as computationally, less attention has been devoted to the heavier selenoxides. In this work, we explore the reductive mechanism of dimethyl selenoxide, as an archetypal selenoxide and, for the sake of comparison, the reductive mechanism of dimethyl sulfoxide to gain insight into the role of the chalcogen on the reaction substrate. Particular attention is devoted to the key role of sulfurane and selenurane intermediates. Moreover, the capacity of these system to oxidize selenols rather than thiols, leading to the formation of selenyl sulfide bridges, is explored in silico. Notably, this analysis provides molecular insight into the role of selenocysteine in methionine sulfoxide reductase selenoenzyme. The activation strain model of chemical reactivity is employed in the studied reactions as an intuitive tool to bridge the computationally predicted effect of the chalcogen on the chalcogenoxide as well as on the chalcogenol.

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Bis(p-methoxyphenyl) Selenoxide as a Mild and Selective Oxidizing Agent

Cited by 38 publications

References 6 publications

Desulfurization with nickel and cobalt boride: scope, selectivity, stereochemistry, and deuterium-labeling studies

Desulfurization with nickel and cobalt boride: scope, selectivity, stereochemistry, and deuterium-labeling studies

Chain‐Breaking Phenolic 2,3‐Dihydrobenzo[b]selenophene Antioxidants: Proximity Effects and Regeneration Studies

The Key Role of Chalcogenurane Intermediates in the Reduction Mechanism of Sulfoxides and Selenoxides by Thiols Explored In Silico

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