Chapter 12

Carbohydrates
 Carbohydrates
• Most sugars have formula Cn(H2O)n, “hydrate
of carbon.”
• Synthesized by plants using sunlight to
convert CO2 and H2O to glucose and O2.
• Polymers include starch and cellulose.
• Starch is storage unit for solar energy.

Chapter 13 2
Classification of Carbohydrates
• Monosaccharides or simple sugars
– polyhydroxyaldehydes or aldoses
– polyhydroxyketones or ketoses
• Disaccharides can be hydrolyzed to two
monosaccharides.
• Polysaccharides hydrolyze to many
monosaccharide units. E.g., starch and
cellulose have > 1000 glucose units.

Chapter 12 3
 Monosaccharides
• Classified by:
– aldose or ketose
– number of carbons in chain
– configuration of chiral carbon farthest from the
carbonyl group (Penultimate carbon)

glucose, a
D-aldohexose

fructose, a
D-ketohexose =>

Chapter 12 4
 D and L Sugars
• D sugars can be degraded to the
dextrorotatory (+) form of glyceraldehyde.
• L sugars can be degraded to the levorotatory
(-) form of glyceraldehyde.

Chapter 12 5
The D Aldose Family

Chapter 23 6
 Epimers
Sugars that differ only in their
stereochemistry at a single carbon.

Chapter 12 7
 Cyclic Structure for Glucose
Glucose cyclic hemiacetal formed by reaction
of -CHO with -OH on C5.

D-glucopyranose
Chapter 12 8
 Cyclic Structure for Fructose
Cyclic hemiacetal formed by reaction of C=O
at C2 with -OH at C5.

D-fructofuranose

Chapter 12 9
Anomers

Chapter 12 10
Mutarotation

Glucose also called

dextrose; dextrorotatory.

Chapter 12 11
 Epimerization
In base, H on C2 may be removed to form
enolate ion. Reprotonation may change
the stereochemistry of C2.

Chapter 12 12
 Reduction of Simple Sugars
• C=O of aldoses or ketoses can be reduced
to C-OH by NaBH4 or H2/Ni.
• Name the sugar alcohol by adding -itol to
the root name of the sugar.
• Reduction of D-glucose produces
D-glucitol, commonly called D-sorbitol.
• Reduction of D-fructose produces a mixture
of D-glucitol and D-mannitol.
Chapter 12 13
 Oxidation by Nitric Acid
Nitric acid oxidizes the aldehyde and the
terminal alcohol; forms aldaric acid.

Chapter 12 14
 Oxidation by Tollens Reagent
• Tollens reagent reacts with aldehyde, but
the base promotes enediol
rearrangements, so ketoses react too.
• Sugars that give a silver mirror with Tollens
are called reducing sugars.

Chapter 12 15
 Nonreducing Sugars
• Glycosides are acetals, stable in base, so they
do not react with Tollens reagent.
• Disaccharides and polysaccharides are also
acetals, nonreducing sugars.

Chapter 23 16
 Formation of Glycosides
• React the sugar with alcohol in acid.
• Since the open chain sugar is in equilibrium
with its - and -hemiacetal, both anomers
of the acetal are formed.
• Aglycone is the term used for the group
bonded to the anomeric carbon.

Chapter 23 17
 Ether Formation
• Sugars are difficult to recrystallize from water
because of their high solubility.
• Convert all -OH groups to -OR, using a
modified Williamson synthesis, after
converting sugar to acetal, stable in base.

Chapter 23 18
 Ester Formation
Acetic anhydride with pyridine catalyst converts
all the oxygens to acetate esters.

Chapter 12 19
 Osazone Formation
Both C1 and C2 react with phenylhydrazine.

Chapter 23 20
 Kiliani-Fischer Synthesis
• This process lengthens the aldose chain.
• A mixture of C2 epimers is formed.

Chapter 12 21
 Fischer’s Proof
• Emil Fischer determined the configuration
around each chiral carbon in D-glucose in 1891,
using Ruff degradation and oxidation reactions.
• He assumed that the -OH is on the right in the
Fischer projection for D-glyceraldehyde.
• This guess turned out to be correct!

Chapter 12 22
 Disaccharides

• Three naturally occurring glycosidic linkages:

• 1-4’ link: The anomeric carbon is bonded
to oxygen on C4 of second sugar.
• 1-6’ link: The anomeric carbon is bonded
to oxygen on C6 of second sugar.
• 1-1’ link: The anomeric carbons of the two
sugars are bonded through an oxygen.

Chapter 12 23
 Cellobiose
• Two glucose units linked 1-4’.
• Disaccharide of cellulose.
• A mutarotating, reducing sugar.

Chapter 12 24
 Maltose
Two glucose units linked 1-4’.

Chapter 12 25
 Lactose
• Galactose + glucose linked 1-4’.
• “Milk sugar.”

Chapter 12 26
 Sucrose
• Glucose + fructose, linked 1-1’
• Nonreducing sugar

Chapter 12 27
 Cellulose

• Polymer of D-glucose, found in plants.

• Mammals lack the -glycosidase enzyme.

Chapter 12 28
 Amylose
• Soluble starch, polymer of D-glucose.
• Starch-iodide complex, deep blue.

Chapter 12 29
 Amylopectin
Branched, insoluble fraction of starch.

Chapter 12 30
 Glycogen
• Glucose polymer, similar to amylopectin, but
even more highly branched.
• Energy storage in muscle tissue and liver.
• The many branched ends provide a quick
means of putting glucose into the blood.

Chapter 12 31
End of Chapter 12

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