Osmium tetroxide metaperiodate

The total synthesis of ( )-geissoschizine (30) was reported by Yamada et al. (156) in 1974. The geometrically pure p-nitrophenyl ester 272 was condensed with tryptamine, and then the resulting amide 273 was transformed to lactam aldehyde 274 by hydroxylation with osmium tetroxide, metaperiodate oxidation, and Pictet-Spengler cyclization. 

Lithium aluminium hydride reduction of 235 followed by mesylation afforded 236. The latter was oxidized with osmium tetroxide and sodium metaperiodate to yield the cyclobutanone 237. Treatment of 237 with acid afforded in 48% yield the ketoacid (238), which was esterified with diazomethane to 239. The latter was converted to the ketal 240 by treatment with ethylene glycol and /7-toluenesulfonic acid. Compound 240 was reduced with lithium aluminium hydride to the alcohol 241. This alcohol had been synthesized previously by Nagata and co-workers (164) by an entirely different route. The azide 242 was prepared in 80% yield by mesylation of 241 and treatment of the product with sodium azide. Lithium aluminium hydride reduction of 242 gave the primary amine, which was converted to the urethane 243 by treatment with ethyl chloroformate. The ketal group of 243 was removed by acidic hydrolysis and the resulting ketone was nitro-sated with N204 and sodium acetate. Decomposition of the nitrosourethane with sodium ethoxide in refluxing ethanol afforded the ketone 244 in 65% yield. The latter had been also synthesized previously by Japanese chemists (165). The ketone 244 was converted to the ketal 246 and the latter to 247... 

The conversion of tetrasubstituted double bonds to the corresponding ketones is easily achieved using a number of oxidants. However, if one or more of the alkenic carbons is secondary, the product will be either an aldehyde or a carboxylic acid Ozone and a combination of osmium tetroxide and sodium metaperiodate are recommended if the desired product is an aldehyde. Under carefully controlled conditions it is also possible to obtain good yields of the aldehyde when permanganate is used as the oxidant All methods that give aldehydes from secondary carbons can also be used to prepare ketones from tertiary carbons. 

Sodium periodate (sodium metaperiodate), NaI04 (mp 300 °C dec), which is commercially available, is applied mainly in aqueous or aqueous-alcoholic solutions. Like the free periodic acid, sodium periodate cleaves vicinal diols to carbonyl compounds [762], This reaction is especially useful in connection with potassium permanganate [763, 764] or osmium tetroxide [765], Such mixed oxidants oxidize alkenes to carbonyl compounds or carboxylic acids, evidently by way of vicinal diols as intermediates. Sulfides are transformed by sodium periodate into sulfoxides [322, 323, 766, 767, 768, 769, 770, 771, 772], and selenides are converted into selenoxides [773]. Sodium periodate is also a reoxidant of lower valency ruthenium in oxidations with ruthenium tetroxide [567, 774],... 

Alternatively, the diester (597) may be oxidised with osmium tetroxide-sodium metaperiodate to the keto-ester (598) which, after reduction of the ketone function by desulphuration of its ethylene thioacetal to give (599), is cyclised and decarboxylated to the unsubstituted ketone (600). 

Sulfones are valuable intermediates for the synthesis of chemically and biologically useful molecules. Traditionally, they are prepared by oxidation of sulfides with nitric acid, KMnO, MnO, NaClO, m-chloroperbenzoic acid, sodium metaperiodate, bromine, dinitrogen tetraoxide, oxaziri-dine, benzeneseleninic peracid, tert-butyl hydroperoxide, sulfinyl peroxy compounds, iodosobenzene diacetate and 4-methylmorpholine N-oxide/ osmium tetroxide. 

---