MONOSACCHARIDES

The monosaccharides are the basis of carbohydrate chemistry since all carbohydrates are either monosaccharides or are converted into monosaccharides on hydrolysis. The monosaccharides are polyhydroxy aldehydes or polyhydroxy ketones. There are, therefore, two main classes of monosaccharides.

1.   The Aldoses, which contain an aldehyde group

2.   The Ketoses, which contain a ketone group –

The aldoses and ketoses are further divided into sub-groups on the basis of the number of carbon atoms in their molecules, as trioses, tetroses, pentoses, hexoses, etc. To classify a monosaccharide completely, it is necessary to specify both, the type of the carbonyl group and the number of carbon atoms present in the molecule. Thus monosaccharides are generally referred to as aldotrioses, aldotetroses, aldopentoses, aldohexoses, ketohexoses, etc.

The aldoses and ketoses may be represented by the following general formulas

Glucose and fructose are specific examples of an aldose and a ketose

Trioses

D and L Terminology:  The simplest of all carbohydrates that fit the definition we have given for carbohydrates are the trioses, glyceraldehyde and dihydroxyacetone. Glyceraldehyde is aldotriose, and dihydroxyacetone is a ketotriose.

Glyceraldehyde cont­ains one asymmetric carbon atom (marked by an asterisk) and can thus exist in two optically active forms, called the D-form and the L-form. Clearly, the two forms are mirror images that cannot be superimposed, that is they are enantiomers.

The two forms of glyceraldehyde are especially important because the more complex monosaccharides may be considered to be derived from them. They serve as a reference point for designating and drawing all other monosaccharides. In carbohydrate chemistry, the Fischer projection formulas are always written with the aldehyde or ketone groups at the top of the structure. By definition, if the hydroxyl group on the asymmetric carbon atom farthest from aldehyde or ketone group projects to the right, the compound is a member of the D-family. If the hydroxyl group on the farthest asymmetric carbon projects to the left, the compound is a member of the L-family. The maximum number of optical isomers of a sugar is related to the number of asymmetric carbon atoms in the molecule and may be calculated by the following simple equation.

Maximum Number of Optical Isomers = 2n, where n = the number of asymmetric carbon atoms.

Since glyceraldehyde contains only one asymmetric carbon atom, the number of optical isomer is 21. We know that 21 is = 2, and we have seen that there are indeed two different glyceraldehydes.

Aldotetroses

If we examine the general formula of an aldotetrose, we see that they contain two asymmetric carbon atoms (marked by asterisks).

This means that 22 or 4 optical isomers are possible. They may be represented as the following two pairs:

All four isomers have been prepared synthetically. The D- and L-erythrose are mirror images, that is, they are enantiomers. They have exactly the same degree of rotation but in  opposite directions. Equal amounts of the two would constitute a racemic mixture, that is, a mixture that would allow a plane-polarised light to pass through the solution unchanged but could be separated into detrorotatory and laevorotatory isomers. The same comments  hold for D- and L-threose. However, D-erythrose and L-threose are not images, that is, they are diastereomers (optical isomers that are not mirror images are called diastereomers), and the degree of rotation of each would probably differ.

Aldopentoses

If we examine the general formula of an aldopentose, we see that they contain three asymmetric carbon atoms.

This means that 23 or 8 optical isomers are possible.  These are: – D(–) xylose, L(+)-xylose, D(–) xylose,  L(–)xylose, D(–) arabinose, L(+)-arabinose,  D(–)-ribose, L(+)-ribose

Aldohexoses

If we examine the general formula of aldohexose, we see that it contains four asymmetric carbon atoms. This means that 24 or 16 optical isomers are possible. D and L forms of altrose, allose  glucose, mannose, galactose, talose, arabinose and idose

Only three of the sixteen possible aldohexoses are found in nature (all sixteen isomers have been prepared synthetically). They are D-glucose, D- mannose, and D-galactose. No one of these three optical iosmers is a mirror image of any of the others, so all three are diastereomers of each other.

Epimers

A pair of diastereomers that differ only in the configuration about of a single carbon atom are said to be epimers. e.g D(+)- glucose is epimeric with D(+) -mannose and D(+) -galactose as shown below

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