D-mannose 392

D (+) Galactose is a constituent of numerous polysaccharides It is best obtained by acid hydrolysis of lactose (milk sugar) a disaccharide of d glucose and d galactose L (—) Galactose also occurs naturally and can be prepared by hydrolysis of flaxseed gum and agar The principal source of d (+) mannose is hydrolysis of the polysaccharide of the ivory nut a large nut like seed obtained from a South American palm... 

It IS not possible to tell by inspection whether the a or p pyranose form of a par ticular carbohydrate predominates at equilibrium As just described the p pyranose form IS the major species present m an aqueous solution of d glucose whereas the a pyranose form predominates m a solution of d mannose (Problem 25 8) The relative abundance of a and p pyranose forms m solution depends on two factors The first is solvation of the anomeric hydroxyl group An equatorial OH is less crowded and better solvated by water than an axial one This effect stabilizes the p pyranose form m aqueous solution The other factor called the anomeric effect, involves an electronic interaction between the nng oxygen and the anomeric substituent and preferentially stabilizes the axial OH of the a pyranose form Because the two effects operate m different directions but are com parable m magnitude m aqueous solution the a pyranose form is more abundant for some carbohydrates and the p pyranose form for others... 

Because Ihe configuralion al C 2 is losl on enolizalion Ihe enediol mlermediale can reverl eilher lo d glucose or lo d mannose Two slereoisomers lhal have mulliple chiralily cenlers bul differ m configuralion al only one of Ihem are referred lo as... 

Treatment of D mannose with methanol in the presence of an acid catalyst yields four iso menc products having the molecular formula C7H14O6 What are these four products ... 

The following are the more stable anomers of the pyranose forms of D glucose D mannose and D galactose... 

Xanthan, although a gum, is derived from the pure culture fermentation of an organism, TCanthomonas campestris. The organism is filtered from the growth medium and the gum recovered by alcohoHc precipitation, followed by drying. It is composed primarily of D-glucose and D-mannose units. 

Gum ghatti is the calcium and magnesium salt of a complex polysaccharide which contains L-arabinose, D-galactose, D-mannose, and D-xylose and D-glucuronic acid (48) and has a molecular weight of approximately 12,000. On dispersion in water, gum ghatti forms viscous solutions of viscosity intermediate between those of gum arabic and gum karaya. These dispersions have emulsification and adhesive properties equivalent to or superior to those described for gum arabic. 

StmcturaHy, guar gum comprises a straight chain of D-mannose with a D-galactose side chain on approximately every other mannose unit the ratio of mannose to galactose is 2 1 (53). Guar gum has a molecular weight on the order of 220,000 (54). 

Goldinonolactone and the tetrahydrofuran moiety of goldinamine were also synthesized from L- and D-mannose, respectively (63). The synthesis of efrotomycin has also been effected (62). 

Because a hexose contains four chiral carbon atoms, there are 2 = 16 different possible arrangements of the hydroxyl groups in space, ie, there are 16 different stereoisomers. The stmctures of half of these, the eight D isomers, are shown in Figure 1. Only three of these 16 stereoisomers are commonly found in nature D-glucose [50-99-7] D-galactose [59-23-4] and D-mannose [3458-28-4]. 

When this isomeiization reaction is catalyzed by alkah, it is termed the Lobry de Bmyn-Alberda van Ekenstein reaction. By it, D-glucose, D-mannose, and D-fmctose can be interconverted. The isomerizations involve a common intermediate, the 1,2-enediol. In the Glu—Man—Fm interconversions... 

Enzymes are specific, however. For example, starch is depolymerized using enzymes to D-glucose (dextrose). The solution of glucose is then treated with glucose isomerase [9055-00-9] to give D-fmctose in about 42% yield. No D-mannose is formed. Addition of isolated D-fmctose to this solution gives the common 55% high fmctose com symp (HFCS) so widely used in soft drinks in the United States. HFCS is about 1.5 times as sweet as sucrose. 

Because the configuration at C-2 is lost on enolization, the enediol intermediate can revert either to D-glucose or to D-mannose. Two stereoisomers that have multiple chirality centers but differ in configuration at only one of them are refened to as... 

D-Allose D-Altrose D-Glucose D-Mannose D-Gulose D-Idose D-Galactose D-Talose... 

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