Oxidation with sodium periodate

Thioanisole (methyl phenyl sulfide) (12.4 g, 0.1 mol) is added to 210 mL (0.105 mol) of a 0.5 M solution of sodium metaperiodate at 0 °C, and the mixture is stirred in an ice bath overnight. The precipitated sodium iodate is filtered, and the filtrate is extracted with chloroform. The extract is dried over anhydrous magnesium sulfate, and the solvents are evaporated under reduced pressure. The residue (13.9 g, 99% yield) is distilled at 83-85 °C at 0.1 mm of Hg to give pure methyl phenyl sulfoxide, mp 29-30 °C. 

Acidic aluminum oxide (Merck 90) for column chromatography (100-325 mesh) (33.4 g) is added in one portion to a magnetically stirred solution of 21.4 g (0.1 mol) of sodium metaperiodate in 60 mL of water at 60 °C. The mixture is stirred for 20 min at 60 °C and then dried in a rotary evaporator. The white residue is heated at 120 °C for 16 h to a constant weight. The concentration of the oxidant is 3 mmol/g of alumina. 

To a solution of 6.2 g (0.05 mol) of methyl phenyl sulfide in 50 mL of 95% ethanol is added 54.8 (0.1 mol) of the supported oxidant in one portion at room temperature. The mixture is stirred vigorously until the sulfide has been completely consumed, as detected by gas-liquid chromatography with a 5% Carbowax 20 M (a polyethylene glycol compound) column (5 h). After filtration of the solid and removal of most of the ethanol by evaporation of the filtrate, 25 mL of dichloro-methane is added. The solution is dried with anhydrous sodium sulfate and evaporated to dryness to give 5.54 g (88%) of methyl phenyl sulfoxide, bp 98-102 °C at 1 mm of Hg. 

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Another interesting conversion of a protoberberine to a rhoeadine skeleton was developed by Murugesan et al. (100). The ketol 176 obtained easily from berberine (15) (Section IV,A,2) was oxidized with sodium periodate to the keto lactone 451, which was transformed to the rhoeadine analogs 452 and 453 by known methods (Scheme 91). Their stereochemistry at the anomeric carbon was not fully clarified. 

Figure 1.106 An N-terminal serine or threonine residue can be oxidized with sodium periodate to produce an aldehyde group. The reaction can be quenched with sodium sulfite to eliminate excess periodate.

Dissolve the macromolecule-containing aldehydes to be blocked (i.e., a glycoprotein that has been oxidized with sodium periodate to create formyl groups) at a concentration... 

Figure 5.35 ABH reacts with aldehyde-containing compounds through its hydrazide end to form hydrazone linkages. Glycoconjugates may be labeled by this reaction after oxidation with sodium periodate to form aldehyde groups. Subsequent photoactivation with UV light causes transformation of the phenyl azide to a nitrene. The nitrene undergoes rapid ring expansion to a dehydroazepine that can couple to nucleophiles, such as amines.

Figure 8.2 Crosslinkers containing a diol group in their cross-bridge design may be cleaved by oxidation with sodium periodate.

Figure 10.3 Antibody molecules oxidized with sodium periodate to create aldehyde groups on their polysaccharide chains can be modified with PDPH to produce thiols after reduction of the pyridyl disulfide. Direct labeling of the sulfhydryls with "Tc produces a radioactive complex.

Figure 20.8 Enzymes that are glycoproteins like HRP may be oxidized with sodium periodate to produce reactive aldehyde residues. Conjugation with an antibody then may be done by reductive animation using sodium cyanoborohydride.

Figure 22.10 Hydroxylic-containing lipid components, such as PG, may be oxidized with sodium periodate to produce aldehyde residues. Modification with amine-containing molecules then may take place using reductive amination.

Figure 23.10 Glycoproteins may be oxidized with sodium periodate to generate aldehyde residues. These may be specifically labeled using a hydrazide-streptavidin derivative through hydrazone bond formation. Subsequent detection may be done using biotinylated enzymes.

Figure 25.12 Dextran polymers can be oxidized with sodium periodate to create a polyaldehyde derivative. Note that additional oxidation may occur to cleave off another carbon atom and create an aldehyde on the adjacent C—OH group.

Lotan, R., Pebray, H., Cacan, M., Cacan, R., and Sharon, N. (1975) Labeling of soybean agglutinin by oxidation with sodium periodate followed by reduction with [3H] borohydride. J. Biol. Chem. 250, 1955-1957. 

The sirup and the crystalline acid (VIII), when oxidized with sodium periodate, gave the same aldehydes as those produced by the oxidation of the ester from D-glucose (II) and its saponification product (XXX), respectively. Hence, the mechanism of the reaction of D-galactose is the same as that of D-glucose and D-mannose. Moreover, the approximate yield from... 

Other Methods of Preparation.—Ethyl 2-formyl-5-methyl-4-furoate has also been prepared by the oxidation of ethyl 2-(D-ara6ino-tetrahydroxybutyl)-5-methyl-4-furoate by means of periodic acid,8 sodium periodate,19 or minium ( red lead ) in acetic acid.66 It can also be prepared by the oxidation with sodium periodate of ethyl 2-(D-lyzo-tetrahydroxybutyl)-5-methyl-4-furoate,15 of ethyl 2-(D-fftreo-trihydroxy-propyl)-5-methyl-4-furoate,13 of ethyl 2-(o-erythro-trihydroxypropyl)-5-methyl-4-furoate,17 of ethyl 2-(L-eryfAro-trihydroxypropyl)-5-methyl-4-furoate,13 and of ethyl 2-(D-goIado-pentahydroxypentyl)-5-methyl-4-furoate.16... 

Periodic acid also oxidises phenols, particularly the ortho compounds. Thus catechol gives o. benzyoquione on oxidation with sodium periodate. 

BODIPY 593/503 C3 hydrazide is 4,4-difluoro-l,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene-8-propionyl hydrazide (Molecular Probes). Unlike BODIPY 530/550 C3 hydrazide, this BODIPY derivative contains substituents that shift to lower wavelengths the spectral characteristics of its fluorescent properties. The molecule is highly reactive toward aldehyde-containing compounds, including glycoproteins that have been oxidized with sodium periodate to create the requisite groups (Fig. 230). 

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