Carbohydrates
• Carbohydrates are the most abundant biomolecules
on Earth.
• They are chemically simpler than nucleotides or
• amino acids, containing just three elements—
carbon, hydrogen, and oxygen—combined
according to the formula (CnH2O)n, where n≥3.
• More complex carbohydrate polymers covalently
attached to proteins or lipids, called as
glycoconjugates
Classes of Carbohydrates
Classified into four major classes:
Monosaccharides - simple sugars consists of a single
polyhydroxy aldehyde or ketone unit. A monosaccharide is a
triose, tetrose, pentose or hexose. The most abundant is D-
Glucose (Dextrose).
Disaccharides - 2 monosaccharides covalently linked.
Oligosaccharides - a few monosaccharides covalently linked
with bond called glycosidic bond.
Polysaccharides - polymers consisting of chains of 20 or more
monosaccharide or disaccharide units.
What is unique about the structures of sugars?
• The building blocks of all carbohydrates are the simple
sugars called monosaccharides.
• The simplest monosaccharides contain three carbon atom
and are called trioses (tri meaning “three”).
• Example of
Glyceraldehyde and
dihydroxyacetone
MONOSACCHARIDES
• These are the simplest sugars and are colorless &
crystalline solids.
• They are either aldoses or ketoses.
• The smallest contain three carbons.
• Monosaccharides Have Asymmetric Centers
• Freely soluble in water.
• Most have a sweet taste.
• C3 – triose, C4 – tetrose, C5 – pentose, C6-hexose, C7 –
heptose.
• Glucose (6-C)
Aldoses
Ketoses
Stereoisomerism in sugars
• Some molecules are not superimposable on their
mirror images and that these mirror images are
stereoisomers (optical isomers) of each other.
• Concept of a chiral (asymmetric) carbon atom.
• The simplest carbohydrate that contains a chiral carbon
is glyceraldehyde.
• Now what would be a dihydroxyacetone? Does this
saccharide contain chiral center?
• The two forms of glyceraldehyde are designated D-
glyceraldehyde and L-glyceraldehyde.
• Fig: D-glyceraldehyde and L-glyceraldehyde.
•Mirror-image stereoisomers are also called
enantiomers, and d-glyceraldehyde and l-
glyceraldehyde are enantiomers of each other
•The D,L system to denote stereochemistry is widely
used by biochemists.
•Organic chemists tend to use a more recent one,
designated the R,S system.
•Here S stands for Sinister" → Latin= "left“ and
R ("Rectus" → Latin= "right")
Fischer projection method
• To show the structures of the resulting molecules, we
need to say more about the convention for a two-
dimensional perspective of the molecular structure.
• In a Fischer projection, bonds written vertically on the
two dimensional paper represent bonds directed behind
the paper in three dimensions.
• Whereas bonds written horizontally represent bonds
directed in front of the paper in three dimensions.
• A molecule with n chiral centers can have 2n
stereoisomers.
•Here vertical bonds show a bond behind paper (dashed)
•Here horizontal bonds show a bond in front (solid)
• Non superimposable, non-mirror-image
stereoisomers are called diastereomers.
• Diastereomers that differ from each other in the
configuration at only one chiral carbon are called
epimers
What happens if a sugar forms a cyclic
molecule?
• Anomers one of the possible stereoisomers formed
when a sugar assumes the cyclic form.
• The cyclization takes place as a result of interaction
between the functional groups on distant carbons,
such as C-1 and C-5, to form a cyclic hemiacetal.
• Another possibility is interaction between C-2 and
C-5 to form a cyclic hemiketal (in ketohexoses).
Fig: Simplest mechanism of Hemiacetal formation
• Sugars, especially those with five or six carbon atoms, normally exist as cyclic
molecules rather than as the open-chain forms we have shown so far. Rings
consisting of five or six carbon atoms are the most stable.
• In ring structure, the carbonyl group forms a covalent bond with the oxygen of a
hydroxyl group along the chain.
• The formation of these ring structures is the result of a general reaction between
alcohols and aldehydes or ketones to form derivatives called hemiacetals or
hemiketals.
• Usually, hemiacetals and hemiketals are formed when an alcohol oxygen atom
adds to the carbonyl carbon of an aldehyde or a ketone.
• Since alcohols are weak nucleophiles, the attack on the carbonyl carbon is
usually promoted by protonation of the carbonyl oxygen.
• Nucleophiles- form binds by donating an electron pair (they are negatively
charged)
• Electrophiles are positively charged species
• Anomeric carbon-the chiral center created when a sugar cyclizes
Fig: Formation of cyclic Hemiacetal
Cyclization of glucose to its hemiacetal form
Haworth projection
• While Fischer projections are used for
sugars in their open-chain form,
• Haworth projections are often used to depict
sugars in their cyclic forms
• Glucose has an aldehyde group and five
hydroxyl groups.
Fig: Conversion of straight chain glucose to glucopyranose
• The cyclic sugars can take either of two different
forms, designated α and β, and are called anomers
of each other.
• The Fischer projection of the α -anomer of a D-
sugar has the anomeric hydroxyl group to the right
of the anomeric carbon (C-OH),
• The β-anomer of a D-sugar has the anomeric
hydroxyl group to the left of the anomeric carbon
Fig: Fischer projection formulas of three forms of glucose
Cyclization of fructose to its hemiketal form
Fig: Conversion of straight chain fructose to frutofuranose
Sugars Can Adopt Different Conformations
• The use of Haworth formulas may lead to the
erroneous impression that furanose and pyranose
rings are planar.
• The pyranose ring, like the cyclohexane ring, can
assume a chair conformation, in which the
substituents of each atom are arranged tetrahedrally.
• Possible chair confirmations are equatorial and axial
configurations
Terminologies
• Constitutional isomers, also known as structural isomers, are specific
types of isomers that share the same molecular formula but have
different bonding atomic organization and bonding patterns.
• Stereoisomers have identical molecular formulas and arrangements of
atoms.
• They differ from each other only in the spatial orientation of groups in
the molecule.
• Non-superimposable Mirror-image of stereoisomers are also called
enantiomers.
• Non superimposable, non-mirror-image stereoisomers are called
diastereomers.
• Epimers are carbohydrates that differ in the location of the -OH group
in one location.. Example is C-2 (from fig).
