Oxone Oxygen, reaction with

The use of dioxiranes (typically DMDO or methyl(trifluoromethyl)dioxirane) as the oxygen-transfer source in epoxidations provides a commonly used and powerful alternative to peracids. The dioxiranes are prepared from the corresponding ketones via reaction with an oxygen-transfer source, usually Oxone (KHSOs) or hydrogen peroxide, the ketone in principle being a catalytic species. 

Sanford and coworkers have reported the use of Oxone in combination with palladium acetate for the oxime-ether directed C-H oxygenation of arenes (eq 111). A range of substituted arenes are tolerated under the reaction conditions and the use of Oxone rather than periodate-based oxidants afforded A -oxidized products in some cases. 

Chiral ketone-catalyzed asymmetric epoxidation has received intensive interest since the first reported by Curci et al. in 1984. The reaction is performed with oxone (potassium peroxomonosulfate) as the primary oxidant which generates the chiral dioxirane catalytic species in situ, which in turn, transfers the oxygen... 

The formal addition of an oxygen atom across the carbonyl group gives rise to dioxiranes (equation 33). In practice, this reaction is effected with Oxone, and dimethyldioxirane (30) and other dioxiranes have been generated in solutions of their parent ketones.Dioxirane (30) has been implicated in oxidations of alkenes, sulfides and iinines. The formal addition of nitrogen across a carbon-oxygen double bond to afford oxaziridines has been reviewed (equation 34).There are also many methods available for the indirect conversion of carbonyl compounds to aziridines > and thiiranes using multi-step conversions. 

Therefore, the classical rrani-dioxoRu(VI) - oxoRu(IV) catalytic cycle [2] (Fig. 1) can be ruled out as the primary reaction pathway in case of rapid catalytic oxygenation. The apparent zero-order kinetics observed are consistent with a steady-state catalytic regime accessible from different initial states of ruthenium metalloporphyrin. Indeed, common oxidants, other than aromatic iV-oxides, such as iodosylbenzene, magnesium monoperoxyphthalate, Oxone and tetrabutylammonium periodate produced the trans-dioxoRu(VI) species from Ru (TPFPP)(CO) under reaction conditions but were ineffective for the rapid catalysis. 

Dimethyldioxirane is a relatively strong oxidant but can show good selectivity its reactivity is similar to that of a peracid but it has the advantage of producing a neutral byproduct (acetone). Methyl(trifluoromethyl)dioxirane is a more powerful oxidant which can insert oxygen into C-H bonds with retention of configuration, as shown below." Dioxiranes are obtained by reaction of ketones with OXONE NOTE Dioxiranes are explosive and are usually handled in dilute solution. 

Ketones and Other Oxygen Functions. Various ketones can be converted to the corresponding dioxiranes by treatment with buffered aqueous solutions of Oxone (eq 1). Of particular interest are dimethyldioxirane (R = R = Me) and methyl(trifluoro-methyl)dioxirane (R = Me, R = CF3) derived from acetone and l,l,l-trifluoro-2-propanone, respectively. The discovery of a method for the isolation of dilute solutions of these volatile dioxiranes in the parent ketone by codistillation from the reaction mixture has opened an exciting new area of oxidation chemistry. Solutions of dioxiranes derived from higher molecular weight ketones have also been prepared. ... 

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