Periodate-Osmium tetroxide

Lemieux-Johnson oxidation, see Periodate-Osmium tetroxide oxidation. 

Periodate-osmium tetroxide oxidation (Lemieux-Johnson). - The reagent, periodate catalyzed by osmium tetroxide, operates as follows. Osmium tetroxide adds to a double bond to form an osmate ester, and this is oxidized by periodate with cleavage to carbonyl compounds and regeneration of osmium tetroxide. Discovery of the... 

Sondheimer et al. used the catalytic method vrith success in another oxidative fission of a Barbier-Wieland diphenylethylene with which ozonolysis and chromic acid oxidation proceeded poorly. Sarel and Yanuka found the method successful as applied to the diphenylethylene (2) with which the periodate-osmium tetroxide method was completely ineffective. The olefinic compound (2) was dissolved in... 

Periodate-Osmium tetroxide oxidation [1, 812-813, after citation of ref. 22]. A British group has reported two cases where cleavage of an exocyclic methylene group is effected more cleanly by this reagent than by ozonolysis.22 ... 

The previously suggested structure (71) for isolongistrobine has been confirmed by synthesis (Scheme 4). TTie amino-alcohol (69) available from related synthetic work (see Vol. 4 of these Reports), was acylated with 4-pentenoyl chloride to give (70), which upon successive oxidation with Cornforth s reagent and oxidative double-bond cleavage with sodium periodate-osmium tetroxide gave isolongistrobine (71)-... 

Related Reagents. Sodium Periodate-Osmium Tetroxide. 

Introduction. Sodium periodate is widely used for the oxidation of a variety of organic substrates and as a cooxidant in other oxidation reactions (see Sodium Periodate-Osmium Tetroxide and Sodium Periodate-Potassium Permanganate) f The Nal04 oxidation is usually conducted in water however, for organic substrates that are insoluble in water, an organic cosolvent (e.g. MeOH, 95% EtOH, 1,4-dioxane, acetone, MeCN) is used. Alternatively, the oxidation can be conducted either with phase-transfer catalysis (PTC) using quaternary ammonium or phosphonium salts in a two-phase system, or in an organic solvent if the oxidant is first coated on an inert support. ... 

The C—C double bond in the cyclopentene ring can be cleaved by the osmium tetroxide-periodate procedure or by photooxygenation. The methoxalyl group on C-17 can, as a typical a-dicarbonyl system, be split off with strong base and is replaced by a proton. Since this elimination occurs with retention of the most stable configuration of the cyclization equi-hbrium, the substituents at C-17 and C-18 are located trans to one another. The critical introduction of both hydrogens was thus achieved regio- and stereoselectively. 

Chemical degradation studies carried out on streptovaricias A and C, which are the primary components of the cmde complex, yielded substances shown ia Figure 1. Streptovaricia A (4), consumes two moles of sodium periodate to yield variciaal A [21913-68-8] (1), 0 2 200, which accounts for the ahphatic portion of the molecule, and prestreptovarone [58074-37-6] (2), C2C)H2C)N02, which accounts for the aromatic chromophore of the streptovaricias (Fig. 2). Streptovaricia G (9) is the only other streptovaricia that yields prestreptovaroae upoa treatmeat with sodium periodate. Treatmeat of streptovaricias A (4), B (5), C (6), E (8), and G (9) with sodium periodate and osmium tetroxide yields streptovarone [36108-44-8] (3), C24H23NO2, which is also produced by the reaction of prestreptovarone with sodium periodate and osmium tetroxide (4,65). A number of aliphatic products were isolated from the oxidation of streptovaricia C and its derivatives (66). 

Osmium tetroxide used in combination with sodium periodate can also effect alkene cleavage.191 Successful oxidative cleavage of double bonds using ruthenium tetroxide and sodium periodate has also been reported.192 In these procedures the osmium or ruthenium can be used in substoichiometric amounts because the periodate reoxidizes the metal to the tetroxide state. Entries 1 to 4 in Scheme 12.18 are examples of these procedures. Entries 5 and 6 show reactions carried out in the course of multistep syntheses. The reaction in Entry 5 followed a 5-exo radical cyclization and served to excise an extraneous carbon. The reaction in Entry 6 followed introduction of the allyl group by enolate alkylation. The aldehyde group in the product was used to introduce an amino group by reductive alkylation (see Section 5.3.1.2). 

In summary, the reaction of osmium tetroxide with alkenes is a reliable and selective transformation. Chiral diamines and cinchona alkakoid are most frequently used as chiral auxiliaries. Complexes derived from osmium tetroxide with diamines do not undergo catalytic turnover, whereas dihydroquinidine and dihydroquinine derivatives have been found to be very effective catalysts for the oxidation of a variety of alkenes. OsC>4 can be used catalytically in the presence of a secondary oxygen donor (e.g., H202, TBHP, A -methylmorpholine-/V-oxide, sodium periodate, 02, sodium hypochlorite, potassium ferricyanide). Furthermore, a remarkable rate enhancement occurs with the addition of a nucleophilic ligand such as pyridine or a tertiary amine. Table 4-11 lists the preferred chiral ligands for the dihydroxylation of a variety of olefins.61 Table 4-12 lists the recommended ligands for each class of olefins. 

If the samples are to be embedded in a resin that is polymerized by UV, such as Lowicryl or LR Gold, do not postfix in osmium tetroxide. Any effect of the osmium on antigenicity can usually be eliminated by using sodium meta-periodate during etching (see step 7). 

Osmium tetroxide used in combination with sodium periodate can also effect alkene cleavage.135 Successful oxidative cleavage of double bonds using ruthenium tetroxide and sodium periodate has also been reported.136 In these procedures, the osmium or ruthenium can be used in substoichiometric amounts because the periodate reoxidizes the metal to the tetroxide state. Entries 1 4 in Scheme 12.17 are examples of these procedures. 

As discussed in connection with cleavage of double bonds by permanganate-periodate or osmium tetroxide-periodate (see p. 757), the glycol unit is susceptible to oxidative cleavage under mild conditions. The most commonly used reagent for this oxidative cleavage is the periodate ion.150 The fragmentation is believed to occur via a... 

There are two syntheses of isoquinolines from indenes by oxidation and subsequent addition of ammonia or ammonium salts, differing only in oxidizing medium. Both are summarized in equation (76) in the first, ozonolysis with a reductive work-up is used (80JOC5312), in the second, periodate and catalytic amounts of osmium tetroxide (81JOC4999). The yields can be very good. 

It is of interest that the methyl alcohol 81 underwent oxidation with chromic acid to afford 3-acetylfervenulin 83 in good yield, whereas the same conditions resulted in the conversion of alcohol 79 into fervenulin 8. The desired product of this latter transformation, that is, fervenulin-3-carboxaldehyde 82, could, however, be obtained, albeit in low yield, by the oxidation of alcohol 79 with manganese dioxide. Fervenulin-3-carboxaldehyde 82 could be obtained in much better yield from the treatment of 3-styrylfervenulin 68 with periodate in the presence of osmium tetroxide, or by ozonolysis of the same substrate. 

Treatment of 53 with DAST [(diethylamino)sulfur trifluoride] in methylene chloride provided 57 in 50% yield. Compound 57 was treated with osmium tetroxide at 5 °C in the presence of NMO (4-methylmopholine N-oxide) for 18 h to provide 58 and 59, which were separated by silica-gel chromatography. Compounds 58 and 59 were treated with sodium periodate at 5 °C for 18 h to provide 60 and 61 respectively. Compounds 60 and 61 were treated with CDsMgl followed by NaB CN to give 62 in 20% and 50% yields, respectively. 

Furo[3,2-c][l]benzopyran-4-ones have been prepared either by acid catalyzed condensation of 4-hydroxycoumarin with a benzoin derivative (equation 11) (81IJC(B)614) or from 3-allyl-4-hydroxycoumarins on oxidation with osmium tetroxide/potassium periodate followed by cyclization of the intermediary aldehyde with PPA (equation 12) (79G109). 

Exercise 16-37 An elegant modification of the two-step procedure to prepare ketones from alkenes by hydroxylation and oxidative cleavage of the diol formed uses a small amount of potassium permanganate (or osmium tetroxide, 0s04) as the catalyst and sodium periodate as the oxidizing agent ... 

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