A. REFRESHING
LECTURE 7
D & L Designation
CARBODYDRATE REACTION The arrangement of the OH's and H's on these atoms is
very important.
Structural formulas for sugar molecules are often written in
the vertical arrangement with the aldehyde or the ketone
group at or near the top.
The sugar is of D (dextro
(dextro)) form when the O H
1C
position of the OH (hydroxyl group) on the
last asymmetric carbon atom (No. 5) is on H 2C OH
the right, the reverse is of L (levo
(levo)) form HO 3C H
D-glucose is an aldohexose with aldehyde H 4C OH
group (red), and the the asymmetric center H 5C OH
(blue) furthest from the aldehyde 6CH OH 2
D-glucose
2
Monosaccharides contain asymmetric carbon
atoms (e.g. 4 in glucose & 2 in ribulose
ribulose))
1 3
H O
1CH2OH
1C
2C O
H 2C OH
4
HO 3C H H 3C OH
H 4C OH H 4C OH
H 5C OH 5CH2OH 5
6CH2OH D-ribulose
D-glucose
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• When a five-
membered ring is
formed, it is called a
furanose
The reactions that lead to the formation of a pyranose or a The a and b anomers
furanose are reversible There are two possible structures for the pyranose and
For example a-D-glucopyranose or b-D-glucopyranose, furanose forms of a monosaccharide, which are called the
these anomers are interconverted to give an equilibrium a- and b-anomers
mixture that is 63.6% of the b-anomer and 36.4% of the a-
anomer.
The 2:1 preference for the b-anomer can be understood by
comparing the structures of these molecules.
In the b-anomer, all of the bulky -OH or -CH2OH substituents lie
+
more or less within the plane of the six-
six-membered ring.
D-ribose -D-ribofuransoe -D-ribofuranose
In the a-anomer, one of the -OH groups is perpendicular to the
plane of the six-
six-membered ring, in a region where it feels strong
repulsive forces from the hydrogen atoms that lie in similar
positions around the ring.
As a result, the b-anomer is slightly more stable than the a-anomer +
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Glycosidic Linkages
The a and b anomers of glucose.
The position of the anomeric
carbon (green
(green or red
red)) relative to
the CH2OH group bound to
carbon 5: they are either on the
(α), or the same
opposite sides (α
(β).
side (β
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C. REACTIONS OF
MONOSACCHARIDES
Carbonyl reactions: Alcohol reactions
Osazone formation Glycoside formation
Cyanohydrin reaction Ether formation
Reduction Ester formation
Oxidation
Action of base
Action of acid
Ring chain tautomerism
Formation of osazones
Osazones are a class of carbohydrate derivatives found in organic
Cyanohydrin formation
chemistry, and formed when sugars are reacted with phenylhydrazine
phenylhydrazine..
The famous German chemist Emil Fischer developed and used the reaction of an aldose with HCN
reaction to identify sugars whose stereochemistry differed by only one used to increase the chain length of monosaccharides
chiral (tangan) carbon
results in a cyanohydrin which is then hydrolyzed to an
A crystalline compound with a sharp melting point will be obtained
acid and reduced to the aldehyde
D-fructose and D-
D-mannose give the same osazone as D- D-glucose
Seldom used for identification; we now use HPLC or mass known as the Fischer-
Fischer-Kiliani synthesis
spectrometry can prepare all monosaccharides from D- D-glyceraldehyde
from mannose
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A hemiketal is an alcohol and ether attached to the same carbon, along with Monosaccharide has just one ring, a disaccharide has two, and a
two other carbons. A hemiketal is derived from a ketone polysaccharide has many
Monosaccharide has a single ring with a hemiacetal in it, a disaccharide has two
rings linked by an acetal functional group, and a polysaccharide has many rings The reaction
between aldehyde
linked by many acetal functional groups.
and alcohol produces
an acetal and a
hemiacetal (about
halfway to the acetal)
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Reduction
either done catalytically (hydrogen and a catalyst)
or enzymatically
the resultant product is a polyol or sugar alcohol
(alditol)
glucose form sorbitol (glucitol)
mannose forms mannitol
fructose forms a mixture of mannitol and
sorbitol
glyceraldehyde gives glycerol
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