MONOSACCHARIDES

- Monosaccharides are the smallest unit of sugars which cannot be further hydrolyzed.

Classification of Monosaccharides
1. According to the number of carbon atoms present
 Triose – contains 3 C atoms
 Tetrose - contains 4 C atoms
 Pentose - contains 5 C atoms
 Hexose - contains 6 C atoms

2. According to the type of carbonyl group present

 Aldoses – monosaccharides that contain CHO (aldehyde) in Carbon 1.
 Ketoses – monosaccharides that contain C=O (ketone) in Carbon 2.
- Example:

O aldehyde (@C1)
II aldose
CH2OH
C–H
I
I ketone (@C2)
ketose C=O
H – C – OH
I
I
HO – C – H
HO – C – H
6 carbon atoms I
I
- both are hexoses H – C – OH
H – C – OH
I
I
H – C – OH
H – C – OH
I
I
CH2OH
CH2OH
D- glucose D-fructose
- We can combine the classification of 2 sugars above by saying D-glucose is an aldohexose, and D-fructose is a ketohexose. Shown
below are the structures of the common monosaccharides:
Aldoses
 Ketoses

Isomerism in Monosaccharides
- Isomers are molecules having the same molecular formula, that is they contain the same elements present and the same number
of atoms for each element. However, their arrangement, connectivity and orientation in space may be different thus, resulting to
different molecules.
- Types of Monosaccharide Isomers
1. Constitutional Isomers – the same molecular formula but different connectivity, different functional groups, and different order of the
bonding atoms
- Example:

O aldehyde (@C1)
II
CH2OH
C–H
I
I
C=O
H – C – OH ketone (@C2)
I
I
HO – C – H
HO – C – H
both have the I
I
molecular formula of H – C – OH
H – C – OH
C6H12O6 I
I
H – C – OH
H – C – OH
I
I
CH2OH
CH2OH
D-glucose D-fructose
- Both sugars have the same molecular formula, C6H12O6. However, since they have different functional groups, and the atoms are
bonded differently, D-glucose and D-fructose are constitutional isomers.

2. Stereoisomers - isomers that have the same structural formula but differ in the orientation of atoms around the molecule, usually in
their stereogenic (chiral) carbons.
- Monosaccharides have often at least 1 and often 2 or more stereogenic carbon.
- A stereogenic (chiral) carbon is an sp3-hybridized (tetrahedral) carbon with four different groups around it.
O
II
C–H
I
H – C – OH
I stereogenic
CH2OH
D-glyceraldehdye

- A compound containing stereogenic carbon is a chiral compound. It demonstrates handedness, a property characterized by mirror
images are not superimposable with each other.
- Types of Stereoisomers:
1. Enantiomers - stereoisomers whose molecules are non-superimposable mirror images of each other.
- Enantiomers can be designated as:
- D – the –OH of the penultimate carbon is directed to the right.
- L – the –OH of the penultimate carbon is directed to the left.
- Example:
O O
II II
C–H C–H
I I
H – C – OH HO – C –H
I I
HO – C – H H – C – OH
I I
H – C – OH HO – C –H
I I
H – C – OH HO – C –H
I I
CH2OH CH2OH
D-glucose L-glucose
- Both molecules have the same order of connectivity of the atoms and they differ only in the orientation of the H and OH groups. Thus,
the two molecules are stereoisomers.
- The two molecules are mirror images of each other wherein the H and OH groups are interchanged in the stereogenic carbons of both
molecules. The mirror images are nonsuperimposable since if the two molecules will be overlapped, the H and OH groups will not
coincide. Thus, the molecules are enantiomers.
- To distinguish the enantiomers from each other, the glucose whose OH of its penultimate carbon is at the right, is named as D-glucose.
The glucose whose OH of its penultimate carbon is at the left is named as L-glucose.
2. Diastereomers – stereoisomers which are not mirror images of each other.
- Example:
O O
II II
C–H C–H
I I
H – C – OH HO – C – H
I I
HO – C – H H – C – OH
I I
H – C – OH H – C – OH
I I
H – C – OH H – C – OH
I I
CH2OH CH2OH
D-glucose D-altrose
- Both molecules have the same order of connectivity of the atoms and they differ only in the orientation of the H and OH groups around
the stereogenic carbons. Thus, the two molecules are stereoisomers.
- The two sugars are not mirror images of each other since not all the H and OH groups are interchanged. Thus, the sugars are
diastereomers.
3. Epimers – diastereomers that differ in the position of only one –OH group.
- Example:
O O
II II
C–H C–H
I I
H – C – OH HO – C –H
I I
HO – C – H HO – C – H
I I
H – C – OH H – C – OH
I I
H – C – OH H – C – OH
I I
CH2OH CH2OH

D-glucose D-mannose
- The two monosaccharides are stereoisomers which are not mirror images of each other. Thus, they are diastereomers. Specifically,
they are also epimers because they differ only in the position of one OH group (enclosed in box).
Fischer Projection: Representation of the Isomerism of Monosaccharides
- It is a 2-D representation of the arrangement of groups around stereogenic carbons which represents the open-chain conformation of
the monosaccharide.
- Using this projection, the monosaccharide is drawn vertically, where the carbonyl group is at or near the top. Counting of carbon
always begin at the top.

O
II
C–H 1 CH2OH
I I
H – C – OH 2 C=O
I I
HO – C – H 3 HO – C – H
I I
H – C – OH 4 H – C – OH
I I
5 H – C – OH
H – C – OH
I I
6
CH2OH CH2OH

D – glucose D - fructose
Monosaccharides of Physiologic Importance
Sugar Location/Production Biochemical Importance
D-ribose Nucleic acids Structural elements of nucleic acids and co
enzymes, e.g. ATP, NAD, NADP, and flavoproteins;
Ribose phosphates are intermediate of pentose
phosphate pathway
D-ribulose Formed in metabolic processes Ribulose phosphates are intermediate of pentose
phosphate pathway
D-arabinose Gum Arabic, plum and cherry gums Constituent of glycoproteins
D-xylose Wood gums, proteoglycans, Constituent of glycoproteins
glycosoaminoglycans
D-lyxose Heart muscle A constituent of lyxoflavin isolated from human heart
muscle
L-xylulose Intermediate in uronic pathway
D-glucose (dextrose) Fruit juices, hydrolysis of starch, cane The “sugar” of the body; This is carried by the blood,
sugar, maltose and lactose and principally used by the tissues.
D-fructose (levulose) Fruit juices, honey, hydrolysis of cane Can be changed into glucose in the liver and so is
sugar and inulin used in the body.
D-galactose Hydrolysis of lactose Can be changed into glucose in the liver and so is
used in the body; synthesized in the mammary gland
to make lactose (milk sugar); a constituent of
glycolipid and glycoproteins.
D-mannose Hydrolysis of plant mannans and gums Constituent of many glycoproteins