Synthesis of the First α‐Methylene‐β‐peroxylactone—Regiospecific Ene Reaction of <sup>1</sup>O<sub>2</sub> with α,β‐Unsaturated Carboxylic Acids

Adam, Waldemar; Griesbeck, Axel G.

doi:10.1002/anie.198510701

Cited by 40 publications

(9 citation statements)

References 5 publications

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“…For alkenes bearing an electron-withdrawing group at the a-position, such as ketone, 95 aldehyde, 96 carboxylic acid, 97 ester, 98 cyano, 96a amide, 96a aldimine, 99 sulfoxide 100 and oxazoline, 101 As part of our continuous interest in the field, we examined the site selectivity in the 1 O 2 ene reaction of alkenes bearing an electron-withdrawing group at the b-position. 103 Some results are summarized in Figure 15.…”

Section: Electron-withdrawing Group At the A-and B-positionmentioning

confidence: 99%

Recent Mechanistic Insights in the Singlet Oxygen Ene Reaction

Alberti¹,

Orfanopoulos²

2010

Synlett

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Singlet oxygen reacts with alkenes, which bear allylic hydrogens, in an ene fashion to afford allylic hydroperoxides. This reaction, apart from its synthetic usefulness, has received extensive mechanistic attention. Numerous experimental studies (e.g., trapping of intermediates, deuterium kinetic isotope effects, regio-or stereoselectivity studies etc.) and to a lesser extend computational work, support a stepwise mechanism with the formation of a threemembered ring (perepoxide-like) intermediate. This Account mainly highlights our group's earlier and recent experimental efforts to ascertain facts relating to this concept.

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Section: Electron-withdrawing Group At the A-and B-positionmentioning

confidence: 99%

Recent Mechanistic Insights in the Singlet Oxygen Ene Reaction

Alberti¹,

Orfanopoulos²

2010

Synlett

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“…To these compounds, 1 O 2 adds preferentially to the bcarbon with concomitant hydrogen abstraction resulting in a-hydroperoxyalkyl acrylate derivatives (Scheme 4). 11 We have now investigated substrates which combine these two effects in order to was converted into trioxanes 20 by Lewis acid catalyzed peroxyacetalization with ketones (Scheme 6). 14 Adamantanone as the carbonyl component gave the spiroperoxide 20a that was also analyzed by X-ray crystal determination.…”

Section: Two Directing Effects: Two Case Studiesmentioning

confidence: 99%

A Family of New 1,2,4-Trioxanes by Photooxygenation of Allylic Alcohols in Sensitizer-Doped Polymers and Secondary Reactions

Bartoschek¹,

El-Idreesy²,

Griesbeck³

et al. 2005

Synthesis

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Type II photooxygenation (singlet oxygen) is described as a synthetically useful way for the preparation of allylic hydroperoxides and endoperoxides using sensitizer-adsorbed or covalently sensitizer-doped polymeric (macro-or nanosized) containers. Facilitated product separation and purification as well as increased reactivity are advantages of these techniques in comparison with solution-phase photochemistry. The products generated by Type II photooxygenation have been used for the syntheses of numerous polycyclic peroxides with a common 1,2,4-trioxane core as exhibited in the natural antimalarial artemisinin.

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“…On the other hand, the related β-peroxylactones were obtained in several other ways (Scheme ) that include photooxidation of α,β-unsaturated carboxylic acids with the subsequent acid-catalyzed cyclization, , photolysis of lactone with (diacetoxyiodo)benzene (DIB), and iodine under oxygen atmosphere and treatment of β-hydroxy esters with H 2 O 2 in the presence of H 2 SO 4 . α-Keto-β-peroxylactone is considered to be an intermediate in oxidation of p -methoxyphenylpyruvic acid by oxygen .…”

Section: Introductionmentioning

confidence: 99%

Five Roads That Converge at the Cyclic Peroxy-Criegee Intermediates: BF₃-Catalyzed Synthesis of β-Hydroperoxy-β-peroxylactones

et al. 2018

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We have discovered synthetic access to βhydroperoxy-β-peroxylactones via BF 3 -catalyzed cyclizations of a variety of acyclic precursors, β-ketoesters and their silyl enol ethers, alkyl enol ethers, enol acetates, and cyclic acetals, with H 2 O 2 . Strikingly, independent of the choice of starting material, these reactions converge at the same β-hydroperoxyβ-peroxylactone products, i.e., the peroxy analogues of the previously elusive cyclic Criegee intermediate of the Baeyer− Villiger reaction. Computed thermodynamic parameters for the formation of the β-hydroperoxy-β-peroxylactones from silyl enol ethers, enol acetates, and cyclic acetals confirm that the β-peroxylactones indeed correspond to a deep energy minimum that connects a variety of the interconverting oxygen-rich species at this combined potential energy surface. The target β-hydroperoxy-β-peroxylactones were synthesized from β-ketoesters, and their silyl enol ethers, alkyl enol ethers, enol acetates, and cyclic acetals were obtained in 30−96% yields. These reactions proceed under mild conditions and open synthetic access to a broad selection of β-hydroperoxy-βperoxylactones that are formed selectively even in those cases when alternative oxidation pathways can be expected. These βperoxylactones are stable and can be useful for further synthetic transformations.

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Synthesis of the First α‐Methylene‐β‐peroxylactone—Regiospecific Ene Reaction of ¹O₂ with α,β‐Unsaturated Carboxylic Acids

Cited by 40 publications

References 5 publications

Recent Mechanistic Insights in the Singlet Oxygen Ene Reaction

Recent Mechanistic Insights in the Singlet Oxygen Ene Reaction

A Family of New 1,2,4-Trioxanes by Photooxygenation of Allylic Alcohols in Sensitizer-Doped Polymers and Secondary Reactions

Five Roads That Converge at the Cyclic Peroxy-Criegee Intermediates: BF₃-Catalyzed Synthesis of β-Hydroperoxy-β-peroxylactones

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Synthesis of the First α‐Methylene‐β‐peroxylactone—Regiospecific Ene Reaction of 1O2 with α,β‐Unsaturated Carboxylic Acids

Cited by 40 publications

References 5 publications

Recent Mechanistic Insights in the Singlet Oxygen Ene Reaction

Recent Mechanistic Insights in the Singlet Oxygen Ene Reaction

A Family of New 1,2,4-Trioxanes by Photooxygenation of Allylic Alcohols in Sensitizer-Doped Polymers and Secondary Reactions

Five Roads That Converge at the Cyclic Peroxy-Criegee Intermediates: BF3-Catalyzed Synthesis of β-Hydroperoxy-β-peroxylactones

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Synthesis of the First α‐Methylene‐β‐peroxylactone—Regiospecific Ene Reaction of ¹O₂ with α,β‐Unsaturated Carboxylic Acids

Five Roads That Converge at the Cyclic Peroxy-Criegee Intermediates: BF₃-Catalyzed Synthesis of β-Hydroperoxy-β-peroxylactones