Periodate-Permanganate

A conveniently short synthesis of a1prostadi1 begins with a mixed aldol assembly of the requisite cyclopentenone 13. This product is then oxidatively cleaved with periodate-permanganate and the alcohol moiety is protected as the tetra-hydropyranyl ether (14). Aqueous chromous sulfate satisfactorily reduces the olefinic linkage and the trans stereoisomer 15 predominates after work-up. The remainder of the synthesis of involves the usual steps, through 16 to with the exception that thexyl tetrahydrolimonyllithium borohydride is used to reduce the C-15 keto moiety so as to produce preferentially the desired C-15S stereochemistry. 

The periodate-permanganate method used was based on a method described previously [105], but three changes from the original published procedure were found to be necessary. A sample size of 50 mg was taken for all oxidations. The same quantities of oxidant, potassium carbonate, and sodium bisulfite (26 ml, 45 mg, 1.06 g, respectively) were used for all samples. An inert marker (5 mg) of methyl palmite or stearate was added to all samples prior to oxidation to serve as a rough check on the completeness of oxidation and the recovery of fragments. 

Several explosive salts including the acetylide, azide, borate, bromate, chlorate, chromate, iodate (and ammonium iodate double salt), nitrite, perchlorate (and ammonium perchlorate double salt), periodate, permanganate, picrate and trinitrobenzoate were prepared. The 3 latter salts and the acetylide, azide and bromate are impact-sensitive detonators [1], It appears probable that many of the explosively unstable compounds [2], formed in various ways from interaction of mercury or its compounds with ammonia or its salts, may have the common polymeric structure now recognised for Millon s base [3], This is a silica-like network of N+ and Hg in 4- and 2-coordination, respectively, with OH and water in the interstitial spaces. Individually indexed compounds are Poly(dimercuryimmonium acetylide)... 

Many names with -ate endings are still allowed, though they are not completely in accord with the derivations outlined above. Some of these are cyanate, dichromate, diphosphate, disulfate, dithionate, fulminate, hypophosphate, metaborate, metaphosphate, metasilicate, orthosilicate, perchlorate, periodate, permanganate, phosphinate, and phos-phonate. The exceptional cases where the names end in -ide or -ite rather than -ate are exemplified below. 

Zinc forms a wide variety of other salts, many by reaction with the adds, though some can only be obtained by fusing the oxides together. The salts include arsenates (ortho, pyro, and meta), the borate, bromate, chlorate, chlorite, various chromates, cyanide, iodate. various periodates, permanganate, phosphates (ortho, pyro, meta, various double phosphates 1. die selenate, selenites, various silicates, fluosilicate. sulfate, sulfite, and duocyanate. 

S-8-S carbon skeleton of Aisicoccins and ophiobolins (equation 10). Trisubstituted alkenes yield keto acids (equation 11). A related reaction, known as the Lemieux-von Rudloff (periodate-permanganate) oxidation, is also used to oxidize alkenes to acids or ketones (equation 12). If aldehydes are required... 

Chloride is often oxidized to chlorine and separated by distillation [3] (see the Methyl Red method). The chloride is oxidized with periodate, permanganate, or cerium(IV), in a sulphuric acid medium, after separation of Br" and T by oxidation to Bt2 and I2 with potassium periodate in dilute HNO3. 

Periodate-Permanganate oxidation [1, 810-812, at end]. In carrying out the oxidation of (R)-(+)-citronellol (8) to the 6-hydroxy-4-methylhexanoic acid (9) by the Lemieux-von Rudloff reagent, Overberger and Kaye16 used acetone-water as the medium in order to conduct the oxidation at a higher concentration. 

Both the 5a- and 5 -A-nor-3-oxapregnanes (145) were obtained when A-norprogesterone was oxidised by periodate-permanganate to the hydroxy-... 

Ring-breaking oxidation is effected with periodate, permanganate, nitric acid, or halogen (basic solution). Proio-quercitol shows anomalous uptake of periodate (8 moles/mole). The products of mild permanganate oxidation, such as deoxyhexaric acids, are useful for characterization. ... 

Lemieux-Rudloff oxidation (1, 810-812). Bernassau and Fetizon have reported a short and efficient degradation of the side chain of lanosterol (1). The first step involves periodate—permanganate oxidation the last step, irradiation... 

Periodate-permanganate aqueous solution of Nal04 (2%, m/v) mixed 2 1 (v/v) with solution of KMn04 (1%, m/v) in aqueous Na2C03 (2%, m/v) Triphenyltetrazolium chloride 2,3,5-triphenyltetrazolium chloride (4%, m/v) in methanol, mixed 1 1 (v/v) with NaOH (1 moll" ) in methanol... 

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