Glycol-cleavage oxidation

II. Mechanism of Glycol-cleavage Oxidation by Lead Tetraacetate. 11... 

Floor, M., Glycol-Cleavage Oxidation of Polysaccharides and Model Compounds Calcium Complexation of Dicarboxy Glucans, Ph.D. thesis, Delft University of Technology, Delft, The Netherlands, 1989. 

The oxidation of cellulose, besides endgroups, may be discussed in three major types as illustrated in Fig. 11. The first type (A) is a glycol cleavage oxidation of a,(3-diol units with periodate giving the dialdehyde derivative... 

Although periodates also oxidize polycyclic aromatic hydrocarbons, phenols, hydrazines, active methylene compounds and sulfides, chemoselectivity can usually be achieved and glycol cleavage oxidation takes precedence. For example, the diol moiety in the diethyl dithioacetal derivative of o-glucose can be selectively oxidized in good yield (equation 6). In contrast, LTA is less selective dum periodate and oxidizes a far greater variety of oiganic compounds. Consequently, in order to minimize undesired reactions, it is customary to add LTA slowly to avoid contact of die initially formed products widi an excess of the oxidant (equation 7). ... 

For many purposes, these oxidants are interchangeable however, the fact that periodate functions best in water, and lead tetraacetate in organic solvents, makes glycol-cleavage oxidation possible with all types of carbohydrates and derivatives. For favorable examples, the behavior of the two reagents toward a given compound is sufficiently different to provide complementary information. 

Several reviews of glycol-cleavage oxidations have appeared. ... 

Historically, developments in chromatography led to a marked growth in research on polysaccharides and carbohydrate-containing biopolymers, which commonly entailed glycol-cleavage oxidation. With time, NMR spectroscopy and mass spectroscopy have acquired complementary roles of ever-increasing importance in studies on molecular structure. 

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