With oxone KHSO

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. 

Recently it has been reported that oxidative cleavage of alkenes with catalytic osmium tetroxide is possible in the absence of water using the co-oxidant Oxone (KHSOs). In this case the diol is not formed and the intermediate osmate ester is oxidized by the Oxone and fragments to regenerate osmium tetroxide and release the carbonyl products. For example, the alkene 1-nonene gave octanoic acid (90% yield) under these conditions. 

The oxidation of aldehydes to carboxylic acids is an important transformation in organic synthesis and several methods have been developed to accomplish this conversion (Srivastava and Venkataramani, 1998). Oxidation of benzaldehydes with oxone (2 KHSO, KHSO, K2S04)/wet-alumina under microwave irradiation in solventless system is a rapid, manipulatively simple, inexpensive and selective protocol. (Nikje and Bigdeli, 2004). 

The direct asymmetric synthesis of a-hydroxy carbonyl derivatives is possible by the use of other methodologies. For instance, the oxidation of silyl enol ethers with oxone (2KHSOj KHSO -KjSO ) in the presence of excess of fructose derivative 62a lead directly to the corresponding chiral a-hydroxy ketones with good enantioselectivities [101]. 

Nitroso compounds are formed selectively via the oxidation of a primary aromatic amine with Caro s acid [7722-86-3] (H2SO ) or Oxone (Du Pont trademark) monopersulfate compound (2KHSO KHSO K SO aniline black [13007-86-8] is obtained if the oxidation is carried out with salts of persulfiiric acid (31). Oxidation of aromatic amines to nitro compounds can be carried out with peroxytrifluoroacetic acid (32). Hydrogen peroxide with acetonitrile converts aniline in a methanol solution to azoxybenzene [495-48-7] (33), perborate in glacial acetic acid yields azobenzene [103-33-3] (34). 

The alkene (5 mmol) and the chiral trifluoroketone, e.g. (+)-3-trifluoroacetylcamphor (4-6 mmol) in CH2C12 (50 ml) are added to aqueous phosphate buffer (pH 7.5, 50 ml), TBA-HS04 (15 mg, 0.04 mmol) and EDTA-Na2 (15 mg). The mixture is stirred at room temperature and aqueous KHSOs (0.6 M, 20 ml) is added slowly over 30-60 min while the pH 7.5 is maintained by the addition of aqueous KOH (1 M). Oxone (15 g) is added over 24 h at room temperature and pH 7.5. The reaction is monitored by GLC and more Oxone is added, if necessary. When complete, the reaction mixture is filtered and the aqueous phase is separated and extracted with CH2C12 (2 x 25 ml) and Et20 (2 x 20 ml). The combined organic solutions are dried (MgS04) and evaporated to yield the oxirane [e.g. 82% l( ,2/ -oxirane from /ran.v-PhCH=CHMe (ee 13%)]. 

Dimethyldioxirane is a powerful oxidant prepared by reacting acetone with KHSOs the latter is commercially available as a triple salt under the trade name of oxone. 1,4-Dinitrocubane... 

Oxone is a registered trademark of DuPont with potassium peroxymonosulfate KHSOs (potassium monopersulfate) as oxidizing ingredient of a triple salt with the formula... 

A number of other oxidants which produce sulfones from sulfoxides are known, such as N02BF4, ° oxygen with Ir or Rh catalysts, ozone,KHSOs (Oxone) and K2S20s. Oxone is a highly chemoselective oxidant for the conversion of sulfides to sulfones without affecting hydroxy or al-kenic groups (equation 37). Similarly flavin (14) oxidizes aryl methyl sulfoxides to sulfones fairly selectively. ... 

Treatment of imine 331 with KHSOs (Oxone) in the presence of NaHC03 afforded A -alkyl oxaziridines 332 in 67-85% yields (Table 26) <2005JOC301>. Optically active oxaziridines of this type could be obtained using phenyl ethylamine as the chiral directing group (Table 26, entries 3 and 4). 

Binding of various metals to polymeric supports or clays has also been utilized to promote reported oxidations. Iron, tin, and tungsten have been reported on clays or on silicon supports. Oxone on SiCb was shown to convert a variety of ketones into esters at room temperature (70-99% conversion typically 98% yield based on conversion). For example, oxidation of 72 with KHSOs-SiC gave lactone 73 in nearly quantitative yield. The authors suggested that the reaction was acid catalyzed by KHSO4 present at the active surface of the reagent.38... 

The third method implies the use of osmium tetroxide and Oxone, and a mixture of 2KHSO5, KjSO and KHSO (Stigers and Tew 2003). With this reaction, a good yield of carboxylation is obtained although a slight degree of backbone degradation was observed. 

---