Oxidation acidic periodate

Cyclic diols give dicarbonyl compounds The reactions are faster when the hydroxyl groups are cis than when they are trans but both stereoisomers are oxidized by periodic acid... 

Alicyclic hydroxamic acids undergo several specific oxidative cleavage reactions which may be of diagnostic or preparative value. In the pyrrolidine series compounds of type 66 have been oxidized with sodium hypobromite or with periodates to give y-nitroso acids (113). Ozonolysis gives the corresponding y-nitro acids. The related cyclic aldonitrone.s are also oxidized by periodate to nitroso acids, presumably via the hydroxamic acids.This periodate fission was used in the complex degradation of J -nitrones derived from aconitine. 

Despite the above-mentioned short-comings, this approach to the estimation of those deoxy sugars which yield malonaldehyde when oxidized with periodate, seemed promising, since, as has been seen (58,59), the dye is formed quantitatively in the reaction of malonaldehyde with 2-thiobarbituric acid also, more recently, its constitution (49,57) and molar extinction coefficient (36) have been established. Thus, if conditions could be found in which malonaldehyde, while being formed quantitatively from the deoxy sugars, would be stable, an ideal method, independent of standard compounds, would be available for the quantitative determination of all of these sugars. 

On the basis of experiments with myoinositol (50), it has been suggested that triose reductone should be oxidized by periodate to yield two molar equivalents of formic acid and one molar equivalent of carbon dioxide. However, it has been reported by two groups (1,29) that crystalline triose reductone is oxidized by two moles of periodic acid to give formic acid and glyoxylic acid, free iodine being liberated during the... 

Crystalline triose reductone has been shown (56) by titration with strong base and with iodine, to exist in solution, for practical purposes, entirely as the enol form. In addition, the fact that it reduces exactly three molar equivalents of periodate to give quantitative yields of formic acid and of carbon dioxide indicates that it is also oxidized entirely in this form. However, nothing is known of the rate of enolization of tartronic dialdehyde and the possibility therefore remains that part of it may be oxidized in the dialdehydo form. If this were the case, the results of periodate oxidations would be dependent on the ratio of the rate of enolization of tartronic dialdehyde to the rate of its oxidation by periodate, since the oxidation of triose reductone is, again, for practical purposes, instantaneous. 

Periodate Oxidation, Acid Hydrolysis, and Structure-Activity Relationships of Human Pituitary, Follicle-Stimulating Hormone, and Human Chorionic Gonadotrophin, J. F. Kennedy, M. F. Chaplin, and M. Stacey, Carbohydr. Res. 36 (1974) 369-377. 

The principal side reaction to epoxide coupling is hydrolysis. Particularly at acid pH values, the epoxide ring can hydrolyze to form adjacent hydroxyls. This diol can be oxidized with periodate to create a terminal aldehyde residue with loss of one molecule of formaldehyde (Chapter 1, Section 4.4). The aldehyde then can be used in reductive amination reactions. The reaction of an epoxide group with an ammonium ion generates a terminal primary amine group that also can be used for further derivatization. 

Sodium periodate also may affect tryptophan residues in some proteins. The oxidation of tryptophan can result in activity losses if the amino acid is an essential component of the active site. For instance, avidin and streptavidin may be severely inactivated by treatment with periodate, since tryptophan is important in forming the biotin-binding pocket. In addition, many other amino acid residues are susceptible to oxidation by periodate (Chapter 1, Section 1.1). Limiting the time of oxidation is important to restricting oxidation to diol groups while not affecting other protein structures. 

In the course of work on the potentiometric titration of some oxidizing acids, Malaprade1 found the existing method for determination of periodic acid in periodic-iodic acid mixtures too inaccurate for estimation of small proportions of one component. He discovered that mannitol will reduce only the periodic acid and, furthermore, that it only reduces the acid to iodic acid.2 The following general reaction appeared to take place. 

The oxidation of the a-amino acids has not been completely studied, but it appears to be slow in most cases.8-9 The organic sulfide linkage is oxidized by periodate to a sulfone, with the concomitant liberation of iodine,48 but the oxidation of a 1-deoxy-l-thioglycoside, without occurrence of this side reaction, has been carried out at least once (in very dilute solution).44... 

As a corollary to this work, oxidation with periodate constitutes the basis of analytical procedures for the determination of 6-deoxyhexoses ( methylpentoses ),88 calcium gluconate89 and gluconic acid,90 hexitols,91 94... 

Simultaneously with the publication of the work of Garda Gonzalez and Sequeiros,29 Jones8 studied the structure of compound XXVI by oxidation with periodic acid. He isolated a crystalline dialdehyde which has the same number of carbon atoms as the starting material. He formulated the dialdehyde as XXXV, and therefore decided that the original acid is XXXII,... 

The tri(D-galactosiduronic acid) 3-glycoside of L-galactonolactone is resistant to the activity of these enzymes. Penta(D-galactosiduronic acid) (1) whose reducing-end unit had been oxidized by periodate was split by the enzyme of Acrocylindrium to oxidized dimer and tri(D-galactosiduronic acid) (3).119... 

D-xylopyranose units. This structural concept is substantiated by estimation of the formic acid obtained when the xylan is oxidized by periodate ions. On hydrolysis of the fully oxidized xylan there is obtained a small amount of D-xylose which presumably occupied the branch points in the polysaccharide and consequently was protected from periodate oxidation by possessing no adjacent free hydroxyl groups. 

Monosaccharide residues containing vicinal hydroxyl groups are oxidized by periodate, and are subsequently removed in the reduction-hydrolysis step. Therefore, the positions to which such monosaccharide residues are linked can be located by methylation analysis performed before, and after, Smith degradation. Alternatively,59 the oxidized and reduced sample is methylated, the ether hydrolyzed, and the product realkylated with CD3I or CH3CH2I. This kind of procedure can have advantages over that first described. For example, methylation before the hydrolysis step hinders the acetal protection of hydroxyl groups that can occur in acid hydrolysis.7... 

Periodic acid oxidation has proved to be a very useful tool in enzymology since a wide variety of biochemicals contain hydroxyl groups on adjacent carbon atoms. For example, periodate-oxidized ATP (also called adenosine 5 -triphosphate 2, 3 -dialdehyde) has often been used as an alternative substrate or an irreversible inhibitor for a wide variety of ATP-utilizing enzymes. This compound, and many others, are now commercially available, even though they are readily synthesized e.g., periodic acid oxidized ADP, AMP, adenosine, P, P -di(adenosine-5 )pentaphosphate, P, P -di(adenosine-5 )tetraphos-phate, GTP, GDP, GMP, guanosine, CTP, CDP, CMP, etc. In the case of the nucleosides, commercial sources also can supply the dialcohol form of the nucleoside i.e., the nucleoside has first been oxidized with periodic acid and then reduced to the dialcohol with borohydride. 

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