A Broadly Applicable Mild Method for the Synthesis of <i>gem</i>-Diperoxides from Corresponding Ketones or 1,3-Dioxolanes

Li, Yun; Hao, Hong-Dong; Zhang, Qi

doi:10.1021/ol900262t

Cited by 68 publications

(37 citation statements)

References 30 publications

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“…[37] Tetraoxane 4. According to a published procedure for preparing gem-dihydroperoxides, [37] ethereal H 2 O 2 (1.44 m, 7 mL, 10 equiv) was added to a stirred mixture of 1-(ethylsulfonyl)piperidin-4-one (383 mg, 2 mmol) and phosphomolybdic acid (73 mg, 2 mol %), and the reaction mixture was stirred for 4 h at room temperature. Et 2 O (15 mL) and H 2 O (5 mL) were added to dilute the reaction mixture.…”

Section: Methodsmentioning

confidence: 99%

Reactions of Antimalarial Peroxides with Each of Leucomethylene Blue and Dihydroflavins: Flavin Reductase and the Cofactor Model Exemplified

et al. 2010

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Flavin adenine dinucleotide (FAD) is reduced by NADPH-E. coli flavin reductase (Fre) to FADH(2) in aqueous buffer at pH 7.4 under argon. Under the same conditions, FADH(2) in turn cleanly reduces the antimalarial drug methylene blue (MB) to leucomethylene blue. The latter is rapidly re-oxidized by artemisinins, thus supporting the proposal that MB exerts its antimalarial activity, and synergizes the antimalarial action of artemisinins, by interfering with redox cycling involving NADPH reduction of flavin cofactors in parasite flavin disulfide reductases. Direct treatment of the FADH(2) generated from NADPH-Fre-FAD by artemisinins and antimalaria-active tetraoxane and trioxolane structural analogues under physiological conditions at pH 7.4 results in rapid reduction of the artemisinins, and efficient conversion of the peroxide structural analogues into ketone products. Comparison of the relative rates of FADH(2) oxidation indicate optimal activity for the trioxolane. Therefore, the rate of intraparastic redox perturbation will be greatest for the trioxolane, and this may be significant in relation to its enhanced in vitro antimalarial activities. (1)H NMR spectroscopic studies using the BNAH-riboflavin (RF) model system indicate that the tetraoxane is capable of using both peroxide units in oxidizing the RFH(2) generated in situ. Use of the NADPH-Fre-FAD catalytic system in the presence of artemisinin or tetraoxane confirms that the latter, in contrast to artemisinin, consumes two reducing equivalents of NADPH. None of the processes described herein requires the presence of ferrous iron. Ferric iron, given its propensity to oxidize reduced flavin cofactors, may play a role in enhancing oxidative stress within the malaria parasite, without requiring interaction with artemisinins or peroxide analogues. The NADPH-Fre-FAD system serves as a convenient mimic of flavin disulfide reductases that maintain redox homeostasis in the malaria parasite.

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Section: Methodsmentioning

confidence: 99%

Reactions of Antimalarial Peroxides with Each of Leucomethylene Blue and Dihydroflavins: Flavin Reductase and the Cofactor Model Exemplified

et al. 2010

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“…Generally all known ozonides are synthesized by ozonolysis of alkenes or by the reaction of O ‐methyl oximes with a carbonyl compound in the presence of ozone . In the literature, there are only few examples of the synthesis of ozonides from carbonyl compounds and hydrogen peroxide …”

Section: Introductionmentioning

confidence: 99%

Catalyst Development for the Synthesis of Ozonides and Tetraoxanes Under Heterogeneous Conditions: Disclosure of an Unprecedented Class of Fungicides for Agricultural Application

Yaremenko

Radulov

Belyakova

et al. 2020

Chemistry A European J

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The catalyst H3+xPMo12−x+6Mox+5O40 supported on SiO2 was developed for peroxidation of 1,3‐ and 1,5‐diketones with hydrogen peroxide with the formation of bridged 1,2,4,5‐tetraoxanes and bridged 1,2,4‐trioxolanes (ozonides) with high yield based on isolated products (up to 86 and 90 %, respectively) under heterogeneous conditions. Synthesis of peroxides under heterogeneous conditions is a rare process and represents a challenge for this field of chemistry, because peroxides tend to decompose on the surface of a catalyst . A new class of antifungal agents for crop protection, that is, cyclic peroxides: bridged 1,2,4,5‐tetraoxanes and bridged ozonides, was discovered. Some ozonides and tetraoxanes exhibit a very high antifungal activity and are superior to commercial fungicides, such as Triadimefon and Kresoxim‐methyl. It is important to note that none of the fungicides used in agricultural chemistry contains a peroxide fragment.

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“…The precursor 1,1-dihydroperoxides are readily available and possess surprising kinetic stability 15,16. The dihydroperoxides of 4- t -butylcyclohexanone and 4-phenyl-2-butanone, 1b and 2b respectively, were prepared in high yield by Re 2 O 7 -catalyzed reaction of the ketones with aq.…”

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confidence: 99%

A New Peroxide Fragmentation: Efficient Chemical Generation of ¹O₂ in Organic Media

Ghorai

Dussault

2009

Org. Lett.

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A Broadly Applicable Mild Method for the Synthesis of gem-Diperoxides from Corresponding Ketones or 1,3-Dioxolanes

Abstract: Ketones or ketals were readily converted into the corresponding gem-dihydroperoxides in high yields by treatment with ethereal H(2)O(2) at ambient temperature in the presence of 2-5 mol % of phosphomolybdic acid.

Cited by 68 publications

References 30 publications

Reactions of Antimalarial Peroxides with Each of Leucomethylene Blue and Dihydroflavins: Flavin Reductase and the Cofactor Model Exemplified

Reactions of Antimalarial Peroxides with Each of Leucomethylene Blue and Dihydroflavins: Flavin Reductase and the Cofactor Model Exemplified

Catalyst Development for the Synthesis of Ozonides and Tetraoxanes Under Heterogeneous Conditions: Disclosure of an Unprecedented Class of Fungicides for Agricultural Application

A New Peroxide Fragmentation: Efficient Chemical Generation of ¹O₂ in Organic Media

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A Broadly Applicable Mild Method for the Synthesis of gem-Diperoxides from Corresponding Ketones or 1,3-Dioxolanes

Abstract: Ketones or ketals were readily converted into the corresponding gem-dihydroperoxides in high yields by treatment with ethereal H(2)O(2) at ambient temperature in the presence of 2-5 mol % of phosphomolybdic acid.

Cited by 68 publications

References 30 publications

Reactions of Antimalarial Peroxides with Each of Leucomethylene Blue and Dihydroflavins: Flavin Reductase and the Cofactor Model Exemplified

Reactions of Antimalarial Peroxides with Each of Leucomethylene Blue and Dihydroflavins: Flavin Reductase and the Cofactor Model Exemplified

Catalyst Development for the Synthesis of Ozonides and Tetraoxanes Under Heterogeneous Conditions: Disclosure of an Unprecedented Class of Fungicides for Agricultural Application

A New Peroxide Fragmentation: Efficient Chemical Generation of 1O2 in Organic Media

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A New Peroxide Fragmentation: Efficient Chemical Generation of ¹O₂ in Organic Media