Recent Advances in the Chemistry of Cyclic Peroxides

McCullough, Kevin J.; Nojima, Màsatomo

doi:10.2174/1385272013375346

Cited by 90 publications

(45 citation statements)

References 167 publications

(214 reference statements)

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“…Most work on 1, 2-dioxole systems has been on derivatives of the fully saturated 1, 2-dioxolane (1) and as cyclic peroxides these have been the subject of three major reviews [1][2][3]. 1,2-Dioxoles are unstable and they have only been detected spectroscopically at temperatures below À60 C [4].…”

Section: Introductionmentioning

confidence: 99%

Five‐Membered Heterocycles with Two Heteroatoms: O and S Derivatives

Wilkins¹

2011

Modern Heterocyclic Chemistry

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Section: Introductionmentioning

confidence: 99%

Five‐Membered Heterocycles with Two Heteroatoms: O and S Derivatives

Wilkins¹

2011

Modern Heterocyclic Chemistry

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“…[7,8] Distonic radical anions can be generated by an electrontransfer (ET) reaction to an endoperoxide. [9,10] These comAbstract: A series of 3,3,6,6-tetraaryl-1,2-dioxanes (TADs) have been investigated at an inert electrode by using cyclic voltammetry, constant potential electrolysis and digital simulations. The series consists of the phenyl-substituted TAD (1 a), p-methoxy-aryl TADs (1 b, 1 c) and the p-methoxy/nitro-bearing TAD (1 d).…”

Section: Introductionmentioning

confidence: 99%

Efficient Homogeneous Radical‐Anion Chain Reactions Initiated by Dissociative Electron Transfer to 3,3,6,6‐Tetraaryl‐1,2‐dioxanes

Stringle

Magri²,

Workentin

2009

Chemistry A European J

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A series of 3,3,6,6-tetraaryl-1,2-dioxanes (TADs) have been investigated at an inert electrode by using cyclic voltammetry, constant potential electrolysis and digital simulations. The series consists of the phenyl-substituted TAD (1 a), p-methoxy-aryl TADs (1 b, 1 c) and the p-methoxy/nitro-bearing TAD (1 d). The heterogeneous electron-transfer (ET) reduction is dissociative, causing rupture of the oxygen-oxygen bond, which generates a distonic radical-anion that reacts competitively either by beta-scission fragmentation or ET. Fragmentation of the distonic radical anion yields an alkene, a substituted benzophenone, and a benzophenone radical anion. The benzophenone radical-anion propagates an efficient homogeneous ET-fragmentation chain reaction that accounts for the potential dependence of the product ratios and the low charge consumption observed in the controlled potential electrolysis experiments. Digital simulation of the experimental cyclic voltammograms allowed for estimates of the rate constants of the heterogeneous ET to the O--O bond, and for the rate constants for the beta-scission fragmentation of the distonic radical-anions. Density functional theory calculations corroborate the differences in the heterogeneous kinetics of the initial dissociative ET. The endoperoxides 1 a-1 c react predominantly by a concerted dissociative ET mechanism, although the data suggests a stepwise dissociative pathway is also competitive. Bearing a nitro-aryl substituent, 1 d provides a rare example of an endoperoxide that proceeds by a stepwise dissociative ET mechanism. Irrespective of the initial mechanistic details, we find a propagating radical-anion cycle is a general mechanistic feature.

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“…[1] They have gained a renaissance in the last 15 years. Artemisinin (qinghaosu) (1) (Scheme 1), a prominent member of this class of compound, exhibits high potency against drug-resistant forms of malaria strains such as Plasmodium falciparum.…”

Section: Introductionmentioning

confidence: 99%

Novel Hydroperoxydioxolanes and ‐dioxanes by Hydroperoxide Rearrangement and Ozonolysis

et al. 2006

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1‐Indanols and 1‐tetralols 8 with alkenyl substituents in the 1‐position have been converted into the corresponding 1‐hydroperoxides 9 by substitution under neutral conditions. Ozonolysis of the products gave rise to the formation of spiro‐1,2‐dioxolane and spiro‐1,2‐dioxane hydroperoxides 12. Alternative treatment of these 1‐indanols and 1‐tetralols 8 with hydrogen peroxide under acidic conditions caused substitution and hydroperoxide rearrangement to yield chroman‐2‐yl hydroperoxides 16 or open‐chain unsaturated geminal bis‐hydroperoxides 21. Ozonolysis of these products resulted in the formation of novel spiro‐chromanes 18 and 20 with two oxygen atoms in the second ring or 3,5‐bis(hydroperoxy)‐1,2‐dioxolanes or 3,6‐bis(hydroperoxy)‐1,2‐dioxanes 23, respectively. All the products showed feeble antimalaria activity against chloroquine‐resistant plasmodium falciparum. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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Recent Advances in the Chemistry of Cyclic Peroxides

Cited by 90 publications

References 167 publications

Five‐Membered Heterocycles with Two Heteroatoms: O and S Derivatives

Five‐Membered Heterocycles with Two Heteroatoms: O and S Derivatives

Efficient Homogeneous Radical‐Anion Chain Reactions Initiated by Dissociative Electron Transfer to 3,3,6,6‐Tetraaryl‐1,2‐dioxanes

Novel Hydroperoxydioxolanes and ‐dioxanes by Hydroperoxide Rearrangement and Ozonolysis

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