Reactions of 2,2'-methylene-bis(cyclohexanone) with hydrogen peroxide and peroxy acids

Kondelíková, Jaroslava; Králíček, Jaroslav; Kubánek, V.

doi:10.1135/cccc19720263

Cited by 11 publications

(6 citation statements)

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“…Encouraged by the large stereoelectronic differences between the otherwise very similar bicyclic bis-peroxides, and the earlier reports of increased stabilities of respective ozonides obtained via different routes [11] , we have investigated reactivity of 1,5-diketones and H2O2. There are only a few scattered literature reports of this process in the presence of P2O5 [12] , V2O5 [13] , and peracetic acid with borone trifluoride. [14] More recently, diketones of oleanane family were transformed into ozonides using a CH3COOOH/H2O2 system.…”

Section: Scheme 1: the Classic And The New Approaches To Ozonide Synthesismentioning

confidence: 99%

Stereoelectronic Control in the Ozone‐Free Synthesis of Ozonides

et al. 2017

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The value of stereoelectronic guidelines is illustrated by the discovery of a convenient, ozone-free synthesis of bridged secondary ozonides from 1,5-dicarbonyl compounds and H O . The tetraoxane products generally formed in reactions of carbonyl and dicarbonyl compounds with H O were not detected because the structural distortions imposed on the tetraoxacyclohexane subunit in [3.2.2]tetraoxanonanes by the three-carbon bridge leads to the partial deactivation of anomeric effects. The new procedure is readily scalable to produce gram quantities of the ozonides. This reaction enables the selective preparation of ozonides without the use of ozone.

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Section: Scheme 1: the Classic And The New Approaches To Ozonide Synthesismentioning

confidence: 99%

Stereoelectronic Control in the Ozone‐Free Synthesis of Ozonides

et al. 2017

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“…The dramatic expansion of medicinal chemistry of organic peroxides was inspired by >100 known peroxide-containing natural products. − The variety of natural examples lessened concerns associated with the perceived peroxide instability and led to research efforts aimed at the development of synthetic approaches to varied classes of cyclic peroxides including 1,2-dioxolanes, − 1,2,4-trioxolanes (ozonides), ,− 1,2-dioxanes, − 1,2,4-trioxanes, − 1,2,4,5-tetraoxanes, − cyclic triperoxides, and tricyclic mono- and bisperoxides. − …”

Section: Introductionmentioning

confidence: 99%

Marriage of Peroxides and Nitrogen Heterocycles: Selective Three-Component Assembly, Peroxide-Preserving Rearrangement, and Stereoelectronic Source of Unusual Stability of Bridged Azaozonides

et al. 2021

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Stable bridged azaozonides can be selectively assembled via a catalyst-free three-component condensation of 1,5-diketones, hydrogen peroxide, and an NH-group source such as aqueous ammonia or ammonium salts. This procedure is scalable and can produce gram quantities of bicyclic stereochemically rich heterocycles. The new azaozonides are thermally stable and can be stored at room temperature for several months without decomposition and for at least 1 year at −10 °C. The chemical stability of azaozonides was explored for their subsequent selective transformations including the first example of an aminoperoxide rearrangement that preserves the peroxide group. The amino group in aminoperoxides has remarkably low nucleophilicity and does not participate in the usual amine alkylation and acylation reactions. These observations and the 15 pK a units decrease in basicity in comparison with a typical dialkyl amine are attributed to the strong hyperconjugative nN→σ*C–O interaction with the two antiperiplanar C–O bonds. Due to the weakness of the complementary nO→σ*C–N donation from the peroxide oxygens (a consequence of “inverse α-effect”), this interaction depletes electron density from the NH moiety, protects it from oxidation, and makes it similar in properties to an amide.

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“…Encouraged by the large stereoelectronic differences between the otherwise very similar bicyclic bisperoxides and earlier reports of the higher stabilities of ozonides obtained by different routes, we investigated the reactivity of 1,5‐diketones and H 2 O 2 . There are only a few scattered reports of this process in the presence of P 2 O 5 , V 2 O 5 , and peracetic acid with borone trifluoride . More recently, diketones of the oleanane family were transformed into ozonides by the use of a CH 3 COOOH/H 2 O 2 system .…”

Section: Figurementioning

confidence: 99%

Stereoelectronic Control in the Ozone‐Free Synthesis of Ozonides

et al. 2017

View full text Add to dashboard Cite

The value of stereoelectronic guidelines is illustrated by the discovery of a convenient, ozone‐free synthesis of bridged secondary ozonides from 1,5‐dicarbonyl compounds and H2O2. The tetraoxane products generally formed in reactions of carbonyl and dicarbonyl compounds with H2O2 were not detected because the structural distortions imposed on the tetraoxacyclohexane subunit in [3.2.2]tetraoxanonanes by the three‐carbon bridge leads to the partial deactivation of anomeric effects. The new procedure is readily scalable to produce gram quantities of the ozonides. This reaction enables the selective preparation of ozonides without the use of ozone.

show abstract

Reactions of 2,2'-methylene-bis(cyclohexanone) with hydrogen peroxide and peroxy acids

Cited by 11 publications

References 0 publications

Stereoelectronic Control in the Ozone‐Free Synthesis of Ozonides

Stereoelectronic Control in the Ozone‐Free Synthesis of Ozonides

Marriage of Peroxides and Nitrogen Heterocycles: Selective Three-Component Assembly, Peroxide-Preserving Rearrangement, and Stereoelectronic Source of Unusual Stability of Bridged Azaozonides

Stereoelectronic Control in the Ozone‐Free Synthesis of Ozonides

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