Glycols oxidation with periodate

Treatment of MFA (1) with cyanogen bromide [6] opened ring G to yield the bromo derivative 3 [7]. Attempts to dehydrobrominate 3 in one step via a base-catalyzed elimination with DBU/CH3CN, KOH/MeOH, or terr-BuOK/DMSO were unsuccessful. However, the required methylene entity could be introduced by converting 3 first to a selenide, then oxidation with periodate, followed by thermolysis in benzene to provide compound 4. Hydrolysis of the cyano group with NaOH in ethylene glycol [8] produced 5 (50% yield). Osmium catalyzed oxidation of 5 in the presence of 4-methylmorpholine A-oxide (NMO) gave a diol, which was cleaved to an aldehyde upon treatment with periodate. Treatment of the aldehyde with sodium cyanoborohydride resulted in an intramolecular reductive animation to yield the desired product PHB (6). 

However, regiopure azido 1,2-diol 19 is converted to the corresponding azido carboxylic acid 22 by oxidative glycol cleavage with periodic acid in the presence of catalytic amounts of ruthenium trichloride. Interestingly, the use of sodium periodate instead of periodic acid resulted in a 10-15 % epimerization of the C-5 stereocenter. 

Certain /S-amino alcohols and glycols and their dehydroderivatives, i.e., a-ketols, a-ketals, and diketones, are readily oxidized with periodic acid or lead tetraacetate to aldehydes. A review of the method has been made. ... 

This alkaloid (CCCXCIII) contains two hydroxyl groups capable of acetylation and a dimethylamino group for which the 20-position was indicated by the occurrence of the peak at m/e 72 in the mass spectrum. On oxidation with periodic acid terminaline yields a dialdehyde. By analogy with the alkaloids of the pachysandrine type the a-glycol moiety was located in position 3,4. This assumption proved to be correct since terminaline on oxidation with periodic acid followed by sodium boro-... 

The formation of a methiodide indicated the tertiary character of the amine, and lack of any oxidation with periodic acid showed that a 1, 2-glycol grouping of two of the oxygens had to be excluded (43). Attempted condensation with nitromethane did not proceed and no reduction product was obtained by the use of sodium amalgam or hydrogen over platinum catalyst. Richardson and Warren also suggested that rosmarinecine was... 

Ethylene and, 2-propylene glycols can be determined simultaneously by oxidation with periodic acid, after distillation, to formaldehyde and acetaldehyde. The reaction proceeds according to the following stoichiometric equations ... 

Secondary hydroxyl groups cannot be determined directly. However, when adjacent hydroxyl groups (a-glycol groups) occur in the molecule, as in 1 —> 4 glucans, they may be determined by oxidation with periodate or lead tetraacetate (see p. 699). Lead tetraacetate oxidations are restricted to nonaqueous solutions, whereas periodate is used for aqueous solutions. One mole of oxidant is consumed for each carbon bond broken. 

In Ref 2 is given the following general equation of oxidation of glycols (compounds with adjacent hydroxyl groups) by periodic acid ... 

The test for ethylene glycol was performed by oxidation of the sample with periodic acid and detection of the resulting formaldehyde with fuchsin-sulfurous acid reagent (9). 

Reagents that specifically oxidize vicinal glycols [e.g., NaI04, Pb-(02CCH3)4, and NaBi03 Section 16-9A] are quite helpful in determining the cyclic structures of sugars. With periodate, the numbers of moles of oxidant consumed and the moles of methanoic acid and methanal produced are... 

The chemical researches were directed towards three main aims. The first dealt with periodic acid oxidation. In 1928, L. Malaprade, at the University of Nancy, hoping to specify the effect of D-mannitol upon the acidity of periodic acid, observed that the carbon-carbon linkages of the polyol were cleaved, and showed that this was a general feature of the specific reaction of periodic acid with a-glycols. Then, P. Fleury had the premonition that this acid should be an invaluable reagent for analytical purposes. He described the utilization and determination of this remarkably selective oxidant, working under mild conditions of pH and temperature. 

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