Fragmentation of chloroperoxides: hypochlorite-mediated dehydration of hydroperoxyacetals to esters

Fisher, Thomas J.; Dussault, Patrick H.

doi:10.1016/j.tetlet.2010.08.068

Cited by 24 publications

(14 citation statements)

References 22 publications

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“…Overall, such an O–O bond cleavage in hydroperoxide or hydroperoxy acetals is exothermic and thermodynamically favored. Rearrangement of hydroperoxides (via the Hock rearrangement mechanism) or hydroperoxy acetals to form corresponding ketones, esters, or lactones are well documented in the literature 11 , 17 . These rearrangements can be catalyzed by metal ions and Lewis acids 18 .…”

Section: Resultsmentioning

confidence: 99%

Singlet oxygen-mediated selective C–H bond hydroperoxidation of ethereal hydrocarbons

2017

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Singlet O2 is a key reactive oxygen species responsible for photodynamic therapy and is generally recognized to be chemically reactive towards C=C double bonds. Herein, we report the hydroperoxidation/lactonization of α-ethereal C–H bonds by singlet O2 (1Δg) under exceptionally mild conditions, i.e., room temperature and ambient pressure, with modest to high yields (38~90%) and excellent site selectivity. Singlet O2 has been known for > 90 years, but was never reported to be able to react with weakly activated C–H bonds in saturated hydrocarbons. Theoretical calculations indicate that singlet O2 directly inserts into the α-ethereal C–H bond in one step with conservation of steric configuration in products. The current discovery of chemical reaction of singlet oxygen with weakly activated solvent C–H bonds, in addition to physical relaxation pathway, provides an important clue to a 35-year-old unresolved mystery regarding huge variations of solvent dependent lifetime of singlet O2.

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Section: Resultsmentioning

confidence: 99%

Singlet oxygen-mediated selective C–H bond hydroperoxidation of ethereal hydrocarbons

2017

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“…The fragmentation of hydroperoxy acetals 178a – e in the presence of Ca(OCl) 2 or t -BuOCl as the catalysts in CH 3 CN generating esters 179a – e proceeds through the Hock-like rearrangement mechanism ( Table 12 ) [ 322 ].…”

Section: Reviewmentioning

confidence: 99%

Rearrangements of organic peroxides and related processes

Yaremenko¹,

Vil²,

Demchuk³

et al. 2016

Beilstein J. Org. Chem.

193

136

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SummaryThis review is the first to collate and summarize main data on named and unnamed rearrangement reactions of peroxides. It should be noted, that in the chemistry of peroxides two types of processes are considered under the term rearrangements. These are conventional rearrangements occurring with the retention of the molecular weight and transformations of one of the peroxide moieties after O–O-bond cleavage. Detailed information about the Baeyer−Villiger, Criegee, Hock, Kornblum−DeLaMare, Dakin, Elbs, Schenck, Smith, Wieland, and Story reactions is given. Unnamed rearrangements of organic peroxides and related processes are also analyzed. The rearrangements and related processes of important natural and synthetic peroxides are discussed separately.

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“…In the 13 C NMR spectra, the signal of the monoperoxyacetal moiety is observed at d 103-113, which is consistent with the known data. 45 The spectra of peroxides 5 show the signal of the tertiary carbon atom of the tert-butylperoxide group at d 79-81. The structures of compounds 7a, 8a, 9a, and 7b, 8b, which were not isolated in the individual state, were unambiguously established by 1 H and 13 C NMR spectroscopy using 2D correlation spectroscopic techniques (COSY, NOESY, editing-HSQC, HSQC-TOCSY, and HMBC).…”

Section: Establishment Of the Structures Of The Synthesized Compoundsmentioning

confidence: 99%

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

et al. 2014

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Fragmentation of chloroperoxides: hypochlorite-mediated dehydration of hydroperoxyacetals to esters

Cited by 24 publications

References 22 publications

Singlet oxygen-mediated selective C–H bond hydroperoxidation of ethereal hydrocarbons

Singlet oxygen-mediated selective C–H bond hydroperoxidation of ethereal hydrocarbons

Rearrangements of organic peroxides and related processes

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

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Fragmentation of chloroperoxides: hypochlorite-mediated dehydration of hydroperoxyacetals to esters

Cited by 24 publications

References 22 publications

Singlet oxygen-mediated selective C–H bond hydroperoxidation of ethereal hydrocarbons

Singlet oxygen-mediated selective C–H bond hydroperoxidation of ethereal hydrocarbons

Rearrangements of organic peroxides and related processes

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

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