One-electron reduction of methyl(trifluoromethyl)dioxirane by iodide ion. Evidence for an electron-transfer chain reaction mediated by the superoxide ion

doi:10.1021/JA00048A002

Paper

One-electron reduction of methyl(trifluoromethyl)dioxirane by iodide ion. Evidence for an electron-transfer chain reaction mediated by the superoxide ion

Published Oct 1, 1992 · W. Adam*, G. Asensio, R. Curci

Journal of the American Chemical Society

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26

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Abstract

One-electron-transfer processes, triggered by I - in catalytic amounts, convert methyl(trifluoromethyl)dioxirane (1) into 1,1,1-trifluoropropanone (trifluoroacetone) and dioxygen. It is proposed that the initially formed bis(oxy)methylene radical anion 1' performs nucleophilic attack at the dioxirane 1, yielding a dimeric radical anion 2'; the latter then fragments into trifluoroacetone and superoxide ion (O 2 .- ). The intermediacy of superoxide ion (the propagator of the electron-transfer chain reaction) is demonstrated by its trapping with either benzoyl chloride or chlorotrimethylsilane

Study Snapshot

Iodide ion catalyzes the electron-transfer chain reaction, converting methyl(trifluoromethyl)dioxirane into 1,1,1-trifluoropropanone and dioxygen, with superoxide ion acting as a propagator.

PopulationOlder adults (50-71 years)

Sample size24

MethodsObservational

OutcomesBody Mass Index projections

ResultsSocial networks mitigate obesity in older groups.

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Paper

One-electron reduction of methyl(trifluoromethyl)dioxirane by iodide ion. Evidence for an electron-transfer chain reaction mediated by the superoxide ion

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References

Citations

Autoinductive conversion of α,α-diiodonitroalkanes to amides and esters catalysed by iodine byproducts under O2.

This study developed a rapid and economical I2/O2-based method for synthesising sterically hindered esters directly from primary nitroalkanes using in situ-generated iodine species.

Heterolytic (2 e) vs Homolytic (1 e) Oxidation Reactivity: N-H versus C-H Switch in the Oxidation of Lactams by Dioxirans.

The nature of the dioxirane determines the oxidation chemoselectivity, with a switch from C-H to N-H oxidation observed in lactam oxidation from dimethyl dioxirane to methyl(trifluoromethyl)dioxirane.

Reactions at interfaces: oxygenation of n-butyl ligands anchored on silica surfaces with methyl(trifluoromethyl)dioxirane.

Dioxirane 1 can effectively oxygenate n-butyl chains bonded to silica surfaces, demonstrating the potential for efficient synthesis of organic compounds with silica-based materials.

Dioxirane Oxidations of Compounds other than Alkenes

Dioxirane oxidations can epoxidize double bonds in cumulenes, oxidize heteroatom functionalities, and Y-H insertions in organometallic compounds.

Kinetic studies on the oxidation of aryl methyl sulfides and sulfoxides by dimethyldioxirane; absolute rate constants and activation parameters for 4-nitrophenyl methyl sulfide and sulfoxide.

The oxidation of aryl methyl sulfides and sulfoxides by dimethyldioxirane obeys second-order kinetics, with the rate of oxidation influenced by the hydrogen bond donor capacity and electron-pair donicity of the solvent.