Carbohydrate
Rezi Riadhi Syahdi, M.Farm
This Chapter Learning
Keypoints
After this lecture, students should be able:
to pinpoint the stucture and conformation of a
carbohydrate molecule using Fischer projection or
Haworth Formula
to describe the reaction that could occur with the
saccharides
to define probable way to chemically synthetize a
simple carbohydrate
to give example of various carbohydrate role in
pharmacy and life
Term carbohydrate comes
from “hydrates of carbon”
Their molecular formula in many were Cn(H2O)m
In modern times, it is more realistic to define a
carbohydrate as a polyhydroxy aldehyde/ketone
Latin word for sugar is saccharum,
hence the term “saccharide” as a
basis for its classification
Monosaccharide simple carbohydrate
It can’t be cleaved into smaller carbohydrated by attempting a hydrolisis
ex: glucose
Disaccharide cleaved into two monosac
ex: sucrose
Oligosaccharide yield 3-10 monosac
ex: raffinose, stachyose
Polysaccharide more than 10 monosac
ex: cellulose
More than 200
monosaccharides are known
Monosaccharide that comes from polyhydroxy aldehyde
aldose
While that comes from polyhydroxy ketones ketose
Evolution of analytical
methods for carbohydrates
Early methods were
primarily colorimetric
methods including the
tests for reducing sugars
employing Cu2+ chemistry
(Benedict’s or Fehling’s
tests)
These tests were also used
to screen for diabetes by
measuring sugar in the
urine (Clinitest reagent)
Structural and projection
Stereochemistry is the key of understanding
carbohydrate structure
Emil Fischer developed a projection formula to
represent stereochemistry in chiral molecules
particularly well suited for carbohydrates
Using glyceraldehyde (2,3-hydroxypropanal) as
fundamental molecule
Orient the aldehyde to be at the top, C2-Hydroxy point
to right in (+)-glyceraldehyde and to left in (-)-
glyceraldehyde
Horizontal bond directed to you
Vertical bond directed to the IP board
Developed by arbitrary method, it was shown to be
correct
Two stereochemical descriptor was used to define this
structure: D used for the molecule which OH is put on
the right, vice versa
Compound that had a spatial arrangement of
substituents analogues to glyceraldehyde were said to
have the D and L configurations, respectively amino
acid
Glyceraldehyde is an aldo
triose
It contains one stereogenic centre two
stereoisomeric forms
Moving up to scale of complexity, exists aldotetrose
contains more than one stereogenic centre
Aldotetrose are the four stereoisomers of 2,3,4-
tryhydroxy butanal
The particular aldotetrosa
shown below is D-erythrose
D and L-Erythrose are two
stereoisomers called enantiomer
There is two others stereoisomer which –OHs group
were located in different sides of each carbon using
fischer projection
They are called threose, D and L-Threose are
enantiomer to each other
Threose is a diastereoisomers to erythrose
More complexity arises when
talking about aldopentoses and
aldohexoses
Aldopentoses have three stereogenic centre 8
stereoisomers, divided into a set of four D-aldopentoses
and four L-aldopentoses
The aldopentoses are named ribose, arabinose, xylose,
lyxose (Ribs are extra lean)
Aldohexoses have 16 possible stereoisomers, 8 belong to
D- series and 8 belong to L series
Most abundant organic compound, D-(+)-glucose is an
aldohexose
All altruist gladly make gum in gallon tanks
Cyclic forms of carbohydrates are
called furanose and pyranose
forms
We remembered that nucleophillic adition of an alcohol
group to a carbonyl group gives a hemiacetal
When the hydroxyl and carbonyl groups are part of the
same molecule, a cyclic hemiacetal is formed
Five membered cyclic hemiacetals are called furanose
forms while six membered are called pyranose forms
Haworth’s formula
Relative configuration of alpha and beta
The configuration is α if the hydroxyl group formed is on
the same side with the highest numbered stereogenic
center in fischer projection
Subtituents that are located in “right” in Fischer
projection will be automatically put “down” in the
corresponding haworth formula
Cyclization occurs in solution to form α
and β anomers
• Hemiacetal formation occurs between anomeric C and another C in the
chain
• The α and β anomers are in equilibrium with open chain form, will
interconvert, but the β anomers are more stable
Cyclic form of pyranose forms
Haworth are satisfactory for
configurational but not for
conformation
X-ray crystallographic studies shows that
pyranose adopts a chair conformation
All ring substituent are equatorial in
beta-D-glucopyranose while only
anomeric hydroxyl group is axial in alpha
isomeric
Therefore beta shows the most stable
chair conformations
Mutarotation is a phenomenon
when a pure anomer form
convert into a balanced mixture
Alpha glucose dissolved in water optic rotation
decreased from 112,2o to 52,6o
Beta glucose dissolced in water optic rotation
increased from 18,7o to 52,6o
Both are converted into a mixture of alpha-beta (36:64)
Ketose
Aldose are more common than ketose, their role also
been more thoroughly studied
Nevertheless some of ketoses also has pivotal point in
life
Ketoses also exist mainly as
hemiacetals
A commonplace variation seen in
carbohydrate is the deoxy sugars
Deoxy sugars have group(s) of hydroxyl that is replaced
by hydrogen
Amino sugar is another
structural variation
The hydroxy is replaced by an amino group
The oldest and most abundant organic compound
in earth is an amino sugar
Glycosides are a large and very
important class of carbohydrate
It is characterized by the replacement of the anomeric
hydroxyl group by some other substituent
Glycosides are named O-glycosides, N-glycosides, S-
glycosides and so on according to the atom attached to
the anomeric carbon
Term glycoside without a
prefix is a O-glycosides
Glycosides also classified as alpha or beta glycosides
according to the configuration at the anomeric carbon
Despite the presence of a number of other hydroxyl groups in the
carbohydrate, only its anomeric is replaced
This is caused by stabilization of the cation by the oxygen in the ring
Disaccharide is a carbohydrate
that yield two monosaccharides
on hydrolisis
Structucally, disaccharides are glycosides in which
alkoxy group is derived from a second sugar molecule
Maltose and cellobiose are isomeric disaccharides, in
which two D-glucopyranoses joined by a glycosidic bond
between C-1 of one unit and C-4 of the other
A single differences cause
maltose and cellobiose differed
significantly in three dimensional
space and behaviour
Maltase is an enzyme that catalyzed the
hydrolytic glycosidic bond of maltose
Emulsin is an enzyme that catalyzed the
hydrolytic cleavage of cellubiose
Maltase also known as an alpha-glucosidase while
emulsin is a beta-glucosidase
Lactose is a beta-glycoside of a D-glucose with a
D-galactose
Sugar (sucrose)
Polysaccharide
Cellulose is a principal stuctural component of
vegetable
Structucally, cellulose is a polysaccharide composed of
several thousand D-glucose joined by a beta(1,4)-
glycosydic linkages
Complete hydrolisis will gives D-glucose
The disaccharides fraction that result from partial
hydrolisis is a cellobiose
• Animals lack the enzymes necessary to catalyze the hydrolisis of
cellulose
• However, there are bacteries in animal guts that could help breaking
down the beta linkage of the glycosides (indirect enzymatic lysis)
• There is a direct source of energy from hydrolisis of a polysaccharide
that comes from alpha-linkage
• Starch (also known as amylum) is a source of energy that has
alpha(1-4)- linkage of glucose as its monomer
Starch is a mixture of a water-
diversible fraction called amylose
and second component called
amylopectin
Amylose is a polysaccharide of alpha(1,4)-linked D-
glucose units
Amylopectin also similar, however it is branched,
attached to C-6 at various points on main chain are 20-
30 glucose units joined by alpha(1,4)-glycosidic bonds
Glycoproteins are protein
molecules that covalently bound
to carbohydrates
The recognization of cell surface in several infection
and the antibody-antigen interaction is involving
glycoprotein
Reduction of carbohydrates
The carbonyl group can be reduced to alcohol functional
group
Typically procedurs using catalytic hydrogenation and
sodium borohydride reduction
The product of sugar reduction called alditol
Oxidation of carbohydrates
Aldehyde is known to be prone to oxidation
A copper(II) sulphate in citric acid (benedict’s reagent)
is capable of oxidizing aliphatic aldehyde to a carboxylic
acid
The formation of a red precipitate copper(I) oxide by
reduction of copper (II) is a positive
Carbohydrate that gives positive result known as
reducing sugar
Aldoses are reducing sugar
Ketoses are also reducing sugars, since it equilibrates as
enediol intermediates
Alpha-hydroxy ketones also give positive results
Any carbohydrate with open chain form also gives
positive result
Benedict reagent is a valuable kit for detecting sugars in
urine
Fehling solution also been used
as test solution for reducing
sugar
A tartrate complex of copper(II) sulphate
Derivates of aldose that is oxidized to carbocylic form is
known as aldonic acid
The reaction with nitric acid
gives aldaric acid
Cyanohydrin formation and
chain extension
Aldehyde is reactive towards nucleophillic adition of
hydrogen cyanide
Killiani Fischer synthesis was known to use this method
Epimerization, isomerization
and retro-aldol cleavage
In aqueous base, a mixture of glucose, fructose, and
mannose resulted from any of them
Two stereisomers with multiple stereogenic but differ at
only one of them is called an epimers
There is another reaction
available to enediol intermediate
Proton transfer from water to C1 may convert enediol
not to an aldose but to a ketose
The isomerization of D-glucose to
D-fructose is an important step in
glycolisis
D-fructose 1,6-phosphate will be
cleaved to two 3 carbon
fragments by aldolase enzym
This reaction known as retro-aldol reaction
Hydroxyl group in carbohydrate
can be acylated and alkylated
The alcohol groups may undergo typical reaction of
hydroxyl function
Ethers are formed under
conditions of Williamson ether
synthesis
Periodic acid oxidation is used
extensively as an analytical
method in carbohydrate
chemistry
The size of the ring could be
identified as five membered (1 :
1 mole) or six membered (2 : 1
mole)
Daftar Pustaka
Francis A. Carrey 4th Organic Chemistry
J. Clayden Organic Chemistry
Garrett and Grisham Biochemistry
