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

Bartoschek, Anna; El-Idreesy, Tamer T.; Griesbeck, Axel G.; Höinck, Lars-Oliver; Lex, Johann; Miara, Claus; Neudörfl, Jörg‐M.

doi:10.1055/s-2005-872103

Cited by 3 publications

(1 citation statement)

References 6 publications

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“…The formation of peroxyketals 342a–g from vicinal hydroxyhydroperoxides 341 (oxidation products of unsaturated alcohols 340 ) in the presence of boron trifluoride is a convenient approach to the synthesis of the 1,2,4-trioxane ring (Scheme 98) [385]. …”

Section: Reviewmentioning

confidence: 99%

Synthesis of five- and six-membered cyclic organic peroxides: Key transformations into peroxide ring-retaining products

Terent’ev¹,

Borisov²,

Vil³

et al. 2014

Beilstein J. Org. Chem.

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SummaryThe present review describes the current status of synthetic five and six-membered cyclic peroxides such as 1,2-dioxolanes, 1,2,4-trioxolanes (ozonides), 1,2-dioxanes, 1,2-dioxenes, 1,2,4-trioxanes, and 1,2,4,5-tetraoxanes. The literature from 2000 onwards is surveyed to provide an update on synthesis of cyclic peroxides. The indicated period of time is, on the whole, characterized by the development of new efficient and scale-up methods for the preparation of these cyclic compounds. It was shown that cyclic peroxides remain unchanged throughout the course of a wide range of fundamental organic reactions. Due to these properties, the molecular structures can be greatly modified to give peroxide ring-retaining products. The chemistry of cyclic peroxides has attracted considerable attention, because these compounds are used in medicine for the design of antimalarial, antihelminthic, and antitumor agents.

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Section: Reviewmentioning

confidence: 99%

Synthesis of five- and six-membered cyclic organic peroxides: Key transformations into peroxide ring-retaining products

Terent’ev¹,

Borisov²,

Vil³

et al. 2014

Beilstein J. Org. Chem.

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1,2,5,10,11,14-Hexaoxadispiro[5.2.5.2]hexadecanes: Novel Spirofused Bis-Trioxane Peroxides

et al. 2008

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A set of new bis-spirofused 1,2,4-trioxanes 4a-d was obtained from the reaction of cyclohexane-1,4-dione with allylic hydroperoxides 2a-d, bearing an additional hydroxy group in the homoallylic position, by diastereoselective photooxygenation of allylic alcohols 1a-d and subsequent BF3-catalyzed peroxyacetalization with the diketone. From the reaction of a monoprotected cyclohexane-1,4-dione 5 with the allylic hydroperoxide 6 derived from the singlet oxygenation of methyl hydroxytiglate, one monospiro compound was obtained, the 1,2,4-trioxane ketone 7, as well as a mixture of the diastereoisomeric syn- and anti bis-1,2,4-trioxanes 8. The structures of bis-1,2,4-trioxanes were examined theoretically by DFT methods and compared with X-ray structural data in order to evaluate the preferential trioxane ring conformational orientation.

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Synthetic Approaches to Mono- and Bicyclic Perortho-Esters with a Central 1,2,4-Trioxane Ring as the Privileged Lead Structure in Antimalarial and Antitumor-Active Peroxides and Clarification of the Peroxide Relevance

et al. 2017

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The synthesis of 4-styryl-substituted 2,3,8-trioxabicyclo[3.3.1]nonanes, peroxides with the core structure of the bioactive 1,2,4-trioxane ring, was conducted by a multistep route starting from the aryl methyl ketones 1a–1c. Condensation and reduction/oxidation delivered enals 4a–4c that were coupled with ethyl acetate and reduced to the 1,3-diol substrates 6a–6c. Highly diastereoselective photooxygenation delivered the hydroperoxides 7a–7c and subsequent PPTS (pyridinium-p-toluenesulfonic acid)-catalyzed peroxyacetalization with alkyl triorthoacetates gave the cyclic peroxides 8a–8e. These compounds in general show only moderate antimalarial activities. In order to extend the repertoire of cyclic peroxide structure, we aimed for the synthesis of spiro-perorthocarbonates from orthoester condensation of β-hydroxy hydroperoxide 9 but could only realize the monocyclic perorthocarbonate 10. That the central peroxide moiety is the key structural motif in anticancer active GST (glutathione S-transferase)-inhibitors was elucidated by the synthesis of a 1,3-dioxane 15—with a similar substitution pattern as the pharmacologically active peroxide 11—via a singlet oxygen ene route from the homoallylic alcohol 12.

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

Cited by 3 publications

References 6 publications

Synthesis of five- and six-membered cyclic organic peroxides: Key transformations into peroxide ring-retaining products

Synthesis of five- and six-membered cyclic organic peroxides: Key transformations into peroxide ring-retaining products

1,2,5,10,11,14-Hexaoxadispiro[5.2.5.2]hexadecanes: Novel Spirofused Bis-Trioxane Peroxides

Synthetic Approaches to Mono- and Bicyclic Perortho-Esters with a Central 1,2,4-Trioxane Ring as the Privileged Lead Structure in Antimalarial and Antitumor-Active Peroxides and Clarification of the Peroxide Relevance

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