Saccharides acidic conditions

The synthetic manipulation of O-glycosylamino acid molecules is usually more complex because they may undergo the acid-catalysed anomerisation of glycosidic bonds (Figure 3.3) and they are also usually more sensitive to acid conditions, due to their aldolic nature (e.g. serine and threonine derivatives). However, the acid-sensitivity is modulated by saccharide and peptide nature. 

It was shown that in buffered solutions binary (boronate Lewis base) complexes as well as ternary (boronate Lewis base saccharide) complexes would be formed. Under acidic conditions these ternary complexes are significant and under certain stoichiometric conditions can become the dominant components in solution. 

These results indicate that, during thermolyses of fructose-containing saccharides, di-D-fructose dianhydrides are formed readily, but subsequent isomerization is extremely slow—even in the presence of added acid. However, under these conditions, the protonating power of any acid is moot. At the high temperatures used, residual water would be driven off rapidly, unless the reaction vessel is pressurized therefore, reaction occurs in the anhydrous melt. It is presumably protonation of one of the ring oxygen atoms in the dianhydrides that constitutes the first step in isomerization, followed by scission of a C-O bond to yield one of the oxocarbenium ion intermediates postulated in Refs. 31 and 80. Such ions have also been postulated as intermediates in the isomerization of spiroketals to a more-stable product. This latter isomerization can be extremely facile 104 dilute aqueous acid,120 or non-aqueous Lewis-acid conditions121 have been used to effect such transformations. 

For the synthesis of carbohydrate-substituted block copolymers, it might be expected that the addition of acid to the polymerization reactions would result in a rate increase. Indeed, the ROMP of saccharide-modified monomers, when conducted in the presence of para-toluene sulfonic acid under emulsion conditions, successfully yielded block copolymers [52]. A key to the success of these reactions was the isolation of the initiated species, which resulted in its separation from the dissociated phosphine. The initiated ruthenium complex was isolated by starting the polymerization in acidic organic solution, from which the reactive species precipitated. The solvent was removed, and the reactive species was washed with additional degassed solvent. The polymerization was completed under emulsion conditions (in water and DTAB), and additional blocks were generated by the sequential addition of the different monomers. This method of polymerization was successful for both the mannose/galactose polymer and for the mannose polymer with the intervening diol sequence (Fig. 16A,B). 

Subjecting monosaccharides to conditions of acid hydrolysis is only of importance in measuring the expected hydrolysis losses during hydrolysis of oligo- and poly-saccharides. Hydrolysis losses may be predicted, based on either the absolute or the relative decomposition of monosaccharides. Absolute decompositions are based on decomposition of monosaccharides. Relative decompositions are based on studies wherein several methods of hydrolysis were applied to the same samples for various lengths of time in this Section, these are classified under the type of acid that causes the least decomposition (that is the largest yield of monosaccharides liberated), because this acid is usually the one of principal concern in the particular study. 

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