3.2 MONOSACCHARIDES

Learning objectives After completing this chapter learner should be able to: understand the structure of monosaccharide becomes familiar with the structure of an aldose and a aketose understand the stereochemistry of monosaccharides.

Structure of Monosaccharides Monosaccharides are polyhydric alcohols containing aldehyde or keto groups. They may be classified into aldoses or ketoses depending upon whether the aldehyde or ketone groups are present. Depending upon the number of carbon atoms they divided into trioses, tetroses, pentoses, hexoses or heptoses. 

STRUCTURE OF MONOSACCHARIDES Sugar - with an aldehyde group - an aldose. - with a keto group - a ketose

Important aldoses in Food Triose Tetrose Pentose Hexose

Structure of important ketoses

Stereochemistry Study of the arrangement of atoms in three-dimensional space. Stereoisomer - compounds in which the atoms are linked in the same order but differ in their spatial arrangement. Carbohydrates exhibit stereoisomerism due to the presence of asymmetric carbon atom in the structure Compounds contain the same number of atoms and the same kinds of group but have different chemical and biological properties.

Asymmetric carbon atom A carbon atom attached to four different atoms or groups Possible stereoisomers where n is the number of asymmetric carbon atoms in a chain molecule the number of isomer is - 2n E.g: Simple sugar -C6H12O6 Glucose has 4 asymmetric carbon atoms (2, 3, 4 & 5). have 24 = 16 stereoisomer -each have identical functional groups - with different spatial configurations. Glucose with 3 asymmetric carbon atoms

Different forms of D-Glucose A - Straight Chain Form B- Ring Form C: Chair Form

Isomerism Monosaccharide exhibits various forms of isomerism due to the presence of asymmetric carbon atom. There are six types of isomerism found with monosaccharides. 1. Aldose-ketose isomerism 2. D&L isomerism 3. Optical isomerism 4. Pyranose and furanose isomerism 5. Alpha and Beta isomerism 6. Epimerism

1. Aldose - Ketose isomerism Sugar -with a keto group- a ketose an an aldehyde group is called an aldose. Fructose has the same molecular formula as glucose but differs in its structural formula, since there is a potential keto group in position 2 of fructose, whereas there is a potential aldehyde group in position 1 of glucose. Ketose

2. D and L isomerism The designation of a sugar isomer as the D form or of its mirror image as the L form is determined by its spatial relationship to the parent compound of the carbohydrate family, the three carbon sugar glyceraldehydes.   The orientation of the -H and -OH groups around the carbon atom adjacent to the terminal primary alcohol carbon determines whether the sugar belongs to the D or L series. When the -OH group on this carbon is on the right, the sugar is a member of the D series; when it is on the left, it is a member of the L series. Most of the monosaccharide occurring in nature is of the D configuration.  

D and L isomers of Glycerose and glucose

3. Optical Isomerism Optical activity When a beam of plane -polarized light is passed through a solution of an optical isomer, it will rotate the direction in which the light is vibrating (plane polarised light) as it passes through them. If rotated to the right -dextrorotatory (+), ‘d’ or to the left - levorotatory (-), ‘l’. The presence of asymmetric carbon atoms confer optical activity on the compound. Optical isomer E.g D.Glucose is dextrorotatory +52.7º D. Fructose is levorotatory -92º

4. Pyranose and Furanose Ring Structures Alcohols react with the carbonyl groups of aldehydes and ketones to form hemiacetals and hemiketals respectively. The hydroxyl and either the aldehyde or the ketone groups of monosaccharide can likewise react intramolecularly to form cyclic hemiacetals and hemiketals.  The configurations of the substitutes of each carbon atom in these sugar rings are conveniently represented by their Haworth’s Projection, in which the heavier ring bonds project in front of the plane of the paper and the lighter ring bonds project behind it. A sugar with a six-member ring is known as pianos in analogy with pram, the simplest compound containing such a ring. Similarly, sugars with five-member rings are furanoses in analogy with furan.

Pyranose and furanose ring structures Pyranose and furanose forms of glucose

Pyranose and furanose forms of Fructose

5. Alpha and Beta Anomers The ring structure of an aldose is a hemiacetal, since it is formed by combination of an adehyde and an alcohol group. Similarly the ring structure of a ketose is hemiketal.

Alpha-Beta anomers of glucose

6. Epimerism Isomers differing as a result of variations in configuration of the OH and -H on carbon atoms 2, 3 and 4 glucose are known as epimers. The most important epimers of glucose are mannose and galactose, formed by epimerization at carbons 2 and 4, respectively

Epimers

3.2.2 Monosaccharide derivatives Monosaccharide units in which an OH group is replaced by other groups are called as monosaccharide derivatives. 1. Glycoside 2. Amino sugar 3. Deoxy sugars

1.Glycosides Glycosides are compounds formed by the condensation reaction between the hydroxyl group of a sugar and the hydroxyl group of a second compound (aglycon) which may or may not be another sugar.  A glycoside produced from glucose is called a glucoside that from galactose is called a galactoside, and so on. Glycosides like the hemiacetals from which they are formed, can exist in both α and ß forms. Glycosides are named by listing the alkyl or aryl group attached to the oxygen, followed by the name of monosaccharide involved, with the suffix-ide appended to it.

Glycosides are named by listing the alkyl or aryl group attached to the oxygen, followed by the name of monosaccharide involved, with the suffix-ide appended to it.