Mild oxidation of
monosaccharides
Mild oxidizing agents like Br2/H2O will
oxidize the CHO in sugars to –onic acids
Eg D-mannose to D-mannonic acid
D-gulose to D-gulonic acid
D-galactose to D-galactonic acid
Example of mild oxidation-Bromine water
CHO CO2H
H OH H OH
HO H Br2/H2O HO H
HO H HO H
H OH H OH
CH2OH CH2OH
D-Galactonic acid
D-Galactose
Strong oxidizing agents
• Strong oxidizing agents like dil.HNO3 will
oxidize both the CHO and last CH2OH in sugars
to –aric acids
• Eg D-mannose to D-mannaric acid
• D-gulose to D-gularic acid
• D-galactose to D-galactaric acid
• D-Idose to D-idaric acid
Nitric acid oxidation of monosacc
CHO CO2H
H OH H OH
HO H dil HNO3 HO H
H OH H OH
H OH H OH
CH2OH CO2H
D-Glucaric acid
D-Glucose
Chain lengthening-Kiliani-Fischer
• This is a process of adding CH2 to a sugar, The
process is called Kiliani-Fischer synthesis.
• Eg transformation of D-arabinose to D-glucose
and D-mannose. In this process HCN is reacted
with D-arabinose to give two cyanohydrins.
The cyanohydrins when reduced with
hydrogen forms two imines which are then
hydrolyzed by acid to D-arabinose and D-
glucose
Kiliani Fischer reaction
• Process of adding CH2 to a sugar
CN CN
CHO
HO H H OH
HO H
HO H HO H
HCN
H OH
H OH H OH
H OH
H OH H OH
CH2OH
D-Arabinose CH2OH CH2OH
cyanohydrin cyanohydrin
Kiliani Fischer reaction
• Reduction of cyano group to imine
CHNH CHNH
CN CN
HO H H OH
HO H H OH
HO H HO H
HO H HO H H2/Pd
H OH H OH
H OH H OH
H OH H OH
H OH H OH
CH2OH CH2OH
CH2OH CH2OH
imine imine
cyanohydrin cyanohydrin
Kiliani Fischer reaction
• Hydrolysis of imine to aldehyde
CHO CHO
CHNH CHNH
HO H H OH
HO H H OH
H3O HO H HO H
HO H HO H
H OH H OH
H OH H OH
H OH H OH
H OH H OH
CH2OH CH2OH
CH2OH CH2OH D-mannose D-glucose
imine imine
Chain-shortening-Wohl Degradation
• This is a process of removing CH2 from a
sugar, The process is called Wohl Degradation.
• Eg transformation of D-galactose to D-lyxose.
In this process H2NOH is reacted with D-
galactose to give an oxime. The oxime is then
dehydrated to cyanohydrin which is finally
base hydrolyzed to D-lyxose
Chain-shortening-Wohl Degradation
• Removal of CH2 from a sugar
CHNOH CN
CHO
H OH H OH
H OH
HO H (CH3CO)2O HO H
HO H H2NOH
HO H CH3CO2ONa HO H
HO H
H OH H OH
H OH
CH2OH CH2OH
CH2OH
D-Galactose oxime Cyanohydrin
D-Galactose
Chain-shortening-Wohl Degradation
• Hydrolysis of cyano to aldehyde
CN
H OH CHO
NaOCH3 HO H
HO H
HO H HO H
H OH H OH
CH2OH CH2OH
Cyanohydrin D-Lyxose
DISACCHARIDES
• These are compounds containing a glycosidic
acetal bond between C1 of the first sugar and
C4 of the second sugar(1-4’-link)
• Eg maltose contains two glucose units. This
can be digested by humans and also be
fermented by yeast. Reducing sugar
• Eg cellobiose contains two glucose units. This
cannot be digested by humans and cannot be
fermented by yeast. Reducing sugar
Maltose structure
• Glycoside joined at C1-C4’: α-connection
CH2OH
O
HO
HO CH2OH
O
HO
O
HO
HO
OH
[4-O(a-D-glucopyranosyl)-a-D-glucopyranose]
Cellobiose structure
• Glycoside joined at C1-C4’:β connection
CH2OH CH2OH
O O
HO O
HO OH
HO
HO HO
[4-O(b-D-glucopyranosyl)-b-D-glucopyranose]
Disaccharides contd
• Eg lactose contains galactose and glucose
units. This occurs in human milk, used in
baking. Reducing sugar
• Eg sucrose contains fructose and glucose
units. Non reducing sugar
Lactose structure
• Glycoside joined at C1-C4’: β-connection
OH
CH2OH CH2OH
O O
O OH
HO
HO
HO HO
[4-O(b-D-galactopyranosyl)-b-D-glucopyranose]
Sucrose structure
• Glycoside joined at C1-C2’: α-connection
CH2OH
O CH2OH
HO
HO
O H
HO OH
O
CH2OH
OH
[2-O(a-D-glucopyranosyl)-b-D-glucofuranoside]
POLYSACCHARIDES
• These are polymers of simple sugars linked
together by glycoside bonds. They are non
reducing.
• Eg starch and cellulose
• In cellulose glycoside bonds are joined by 1-4’-
beta-glycoside bonds
Cellulose structure
• Glycosides joined at C1-C4’: beta-connection
O CH2OH CH2OH
O
O CH2OH
HO O O
HO HO O
HO O
HO
cellulose HO
1,4'-O-(b-D-glucopyranoside)polymer
Nature uses cellulose as a
structural material to impart
strength and rigidity to plants.
Wood, leaves, grasses, and cotton
are primarily cellulose. It can also
be used to prepare cellulose
acetate(rayon). In this all OH
groups are acetylated ie OH to
CH3COO-----
Cellulose contd
• Uses:
• structural materials
• Cellulose acetate manufacture
• Furniture
• Paper
• clothing-cotton
STARCH
• In starch glycoside bonds are joined by 1-4’-
alpha-glycoside bonds. We have soluble
starch(amylopectin); and insoluble
starch(amylose)
• Starch containing: potatoes, corn,maize, millet
etc
• Amylose accounts for 20%
Structure of amylose
• Glycoside joined at C1-C4’: α-connection
CH2OH
O O
HO
HO CH2OH
O
O
HO CH2OH
O
HO
O
HO
Amylose HO
O
1,4'-O-(a-D-glucopyranoside)polymer
Starch contd
• Amylopectin accounts for 80% of starch
• The structure here is more complex.
• Here glycoside bonds are joined by 1,4’-links
and 1,6’-links. This will give rise to cross-
linking of the chains after about 25 glucose
units.
Structure of amylopectin
• Glycoside joined at C1-C4’: cross-linking at C1-
C6’ O
O
CH2OH
O O
HO
O
HO H2 C
O
O
HO CH2OH
O
HO
O
HO
Amylopectin HO
O
1,4'-O-(a-D-glucopyranoside)polymer
When eaten starch is digested in
the mouth and stomach by
enzymes called glycosidases, which
catalyze the hydrolysis of glycoside
bonds. Glycosidases only hydrolyze
alpha-glycoside bonds in starch
and leave beta-glycoside bonds in
cellulose.
Glycogen
• This is also a polymer of glucose. It contains a
3-dimensional structure with both 1,4’-links
and 1,6’-links. The chain from main chain may
also have a cross link.
• Glycogen molecule is larger than amylopectin.
It may have up to 100,000 glucose units
Structure of glycogen
• Additional cross linking at C1-C4, C1-C6
O
O
CH2OH
O O O
HO CH2
O
HO O
CH2 O
O
HO CH2OO
HO
O
HO
Glycogen HO
O
1,4'-O-(a-D-glucopyranoside)polymer
Other sugars
• Deoxy sugars eg 2-Deoxyribose in DNA
• Amino sugars eg glucosamine-one OH
replaced with NH2 in glucose
• Glycoproteins-polysaccharides covalently
bonded to OH on proteins via glycosidic bond
• This acts as a biochemical label on cell
surfaces in determination of blood groups
Deoxy sugar structure
• This sugar found in RNA
HOH2C
O OH
OH
Glucosamine structure
• B=beta
CH2OH
O
HO OH
HO
H2N
b-D-glucosamine
Blood groups
• Group O: protein-N-acetylglucosamine-
galactose-fucose
• Group A: protein-N-acetylglucosamine-
galactose-fucose-N-acetyl galactosamine
• Group B: protein-N-acetylglucosamine-
galactose-fucose-galactose
• Group AB: protein-N-acetylglucosamine-
galactose-fucose-N-acetyl galactosamine
Other carbohydrates
• B=beta
HO OH
CH2OH
O
OH O OH
HO
H3C
H3COCHN
HO a-L-fucose
b-D-N-acetylgalactosamine
OH
Other carbohydrates contd
• B=beta
CH2OH
O
CH2OH HO OH
O HO
HO OH
HO H3COCHN
H2N b-D-N-acetylglucosamine
b-D-glucosamine
•END
