Reactions of mono- and bicyclic enol ethers with the I<sub>2</sub>–hydroperoxide system

Terent’ev, Alexander O.; Zdvizhkov, Alexander T.; Kulakova, Alena N.; Новиков, Роман А.; Arzumanyan, Ashot V.; Nikishin, G. I.

doi:10.1039/c3ra46462h

Cited by 12 publications

(9 citation statements)

References 117 publications

(24 reference statements)

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“…We initiated our study by using 1 (0.4 mmol, 1 equiv) with TBHP (3 equiv) and NIS (1 equiv) in diethyl ether as solvent at room temperature (entry 1, table 1) to observe the formation of two products, the desired α‐tert‐butoxyglycoside (1a) and 2‐iodoglucose hemiacetal (2a), almost in equal proportion as confirmed by spectroscopic analysis. This was in contrast to the iodoperoxide product obtained by the reaction of enol ethers other than glycals under similar conditions used by Alexander et al …”

Section: Resultscontrasting

confidence: 58%

Reaction of Glycals with Organic Peroxides: Synthesis of 2-iodo, 2-Deoxy and 2,3-Unsaturated Glycosides

et al. 2016

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Reaction of peroxides with glycals, when carried in the presence of NIS affords2‐deoxy‐2‐iodo‐α‐glycosides in good yields with predominant trans‐diaxial selectivity at rt. Under photolytic conditions in the presence of catalytic eosin Y, the reaction leads to 2‐deoxyglycosides or 2,3‐unsaturated‐α‐glycosides. NIS plays two roles firstly, to form an iodonium ion with the glycal and secondly to bring about the decomposition of the organic peroxide into an alcohol that reacts with the activated sugar whereas blue LED light and Eosin Y bring about a radical‐mediated glycosylation to give the α‐2‐deoxy glycoside or 2,3‐unsaturated glycosides based on the protecting group at C‐3 position of glycals.

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Section: Resultscontrasting

confidence: 58%

Reaction of Glycals with Organic Peroxides: Synthesis of 2-iodo, 2-Deoxy and 2,3-Unsaturated Glycosides

et al. 2016

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“…These comprise the widely used Lewis acids AlCl 3 and the tin(II) and tin(IV) chlorides, which proved to be effective catalysts for the preparation of geminal bishydroperoxides and cyclic triperoxides . Also the aprotic I 2 was employed, which proved useful for the peroxidation of alkenes, enol esters, and acetals . Moreover, we tested heteropoly acidsphosphomolybdic and phosphotungstic acidswhich were previously shown to be effective catalysts for the peroxidation of carbonyl compounds .…”

Section: Results and Discussionmentioning

confidence: 99%

“…45 Also the aprotic I 2 was employed, which proved useful for the peroxidation of alkenes, enol esters, and acetals. 46 Moreover, we tested heteropoly acidsphosphomolybdic and phosphotungstic acidswhich were previously shown to be effective catalysts for the peroxidation of carbonyl compounds. 47 The strong Bronsted acids p-TsOH, H 2 SO 4 , and HClO 4 traditional protic catalysts in preparative peroxidation chemistry 48 were as well tried.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Lanthanide-Catalyzed Oxyfunctionalization of 1,3-Diketones, Acetoacetic Esters, And Malonates by Oxidative C–O Coupling with Malonyl Peroxides

et al. 2016

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The lanthanide-catalyzed oxidative C-O coupling of 1,3-dicarbonyl compounds with diacyl peroxides, specifically the cyclic malonyl peroxides, has been developed. An important feature of this new reaction concerns the advantageous role of the peroxide acting both as oxidant and reagent for C-O coupling. It is shown that lanthanide salts may be used in combination with peroxides for selective oxidative transformations. The vast range of lanthanide salts (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Y) catalyzes oxidative C-O coupling much more efficiently than other used Lewis and Bronsted acids. This oxidative cross-coupling protocol furnishes mono and double C-O coupling products chemo-selectively in high yields with a broad substrate scope. The double C-O coupling products may be hydrolyzed to vicinal tricarbonyl compounds, which are otherwise cumbersome to prepare. Based on the present experimental results, a nucleophilic substitution mechanism is proposed for the C-O coupling process in which the lanthanide metal ion serves as Lewis acid to activate the enol of the 1,3-dicarbonyl substrate. The side reactions-chlorination and hydroxylation of the 1,3-dicarbonyl partners-may be minimized under proper conditions.

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“…Peroxidation of monocyclic enol ethers 256 under the action of the I 2 /H 2 O 2 system proceeded with the formation of iodo-hydroperoxides 257 and α-iodo hemiacetals 258, while the reaction with I 2 /ROOH led only to iodoperoxides 259 (Scheme 94) [192]. The application of I2/H2O2 and I2/TBHP systems to non-aromatic aldehydes allows one to obtain hydroxy-hydroperoxides 248 and tert-butylhydroxyperoxides 249 (Scheme 92) [190].…”

Section: Iodine In the Synthesis Of Organic Peroxidesmentioning

confidence: 99%

Lewis Acids and Heteropoly Acids in the Synthesis of Organic Peroxides

et al. 2022

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Organic peroxides are an important class of compounds for organic synthesis, pharmacological chemistry, materials science, and the polymer industry. Here, for the first time, we summarize the main achievements in the synthesis of organic peroxides by the action of Lewis acids and heteropoly acids. This review consists of three parts: (1) metal-based Lewis acids in the synthesis of organic peroxides; (2) the synthesis of organic peroxides promoted by non-metal-based Lewis acids; and (3) the application of heteropoly acids in the synthesis of organic peroxides. The information covered in this review will be useful for specialists in the field of organic synthesis, reactions and processes of oxygen-containing compounds, catalysis, pharmaceuticals, and materials engineering.

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Reactions of mono- and bicyclic enol ethers with the I₂–hydroperoxide system

Abstract: Reactions of mono- and bicyclic enol ethers with I2–H2O2, I2–ButOOH, and I2–tetrahydropyranyl hydroperoxide systems possessing unique and unpredictable reactivity have been studied.

Cited by 12 publications

References 117 publications

Reaction of Glycals with Organic Peroxides: Synthesis of 2-iodo, 2-Deoxy and 2,3-Unsaturated Glycosides

Reaction of Glycals with Organic Peroxides: Synthesis of 2-iodo, 2-Deoxy and 2,3-Unsaturated Glycosides

Lanthanide-Catalyzed Oxyfunctionalization of 1,3-Diketones, Acetoacetic Esters, And Malonates by Oxidative C–O Coupling with Malonyl Peroxides

Lewis Acids and Heteropoly Acids in the Synthesis of Organic Peroxides

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Reactions of mono- and bicyclic enol ethers with the I2–hydroperoxide system

Abstract: Reactions of mono- and bicyclic enol ethers with I2–H2O2, I2–ButOOH, and I2–tetrahydropyranyl hydroperoxide systems possessing unique and unpredictable reactivity have been studied.

Cited by 12 publications

References 117 publications

Reaction of Glycals with Organic Peroxides: Synthesis of 2-iodo, 2-Deoxy and 2,3-Unsaturated Glycosides

Reaction of Glycals with Organic Peroxides: Synthesis of 2-iodo, 2-Deoxy and 2,3-Unsaturated Glycosides

Lanthanide-Catalyzed Oxyfunctionalization of 1,3-Diketones, Acetoacetic Esters, And Malonates by Oxidative C–O Coupling with Malonyl Peroxides

Lewis Acids and Heteropoly Acids in the Synthesis of Organic Peroxides

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Reactions of mono- and bicyclic enol ethers with the I₂–hydroperoxide system