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Chapter 12Carbohydrates
Chapter 13 2
Carbohydrates
• 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.• Most sugars have formula Cn(H2O)n, “hydrate
of carbon.”
Chapter 12 3
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 4
Monosaccharides• Classified by:
– aldose or ketose– number of carbons in chain– configuration of chiral carbon farthest from the
carbonyl group
glucose, a D-aldohexose
fructose, a D-ketohexose =>
Chapter 12 5
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 23 6
The D Aldose Family
Chapter 12 7
EpimersSugars that differ only in their
stereochemistry at a single carbon.
Chapter 12 8
Cyclic Structure for GlucoseGlucose cyclic hemiacetal formed by reaction
of -CHO with -OH on C5.
D-glucopyranose
Chapter 12 9
Cyclic Structure for FructoseCyclic hemiacetal formed by reaction of C=O
at C2 with -OH at C5.
D-fructofuranose
Chapter 12 10
Anomers
Chapter 12 11
Mutarotation
Glucose also called dextrose; dextrorotatory.
Chapter 12 12
EpimerizationIn base, H on C2 may be removed to form
enolate ion. Reprotonation may change the stereochemistry of C2.
Chapter 12 13
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 14
Oxidation by Nitric AcidNitric acid oxidizes the aldehyde and the
terminal alcohol; forms aldaric acid.
Chapter 12 15
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 23 16
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 17
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 18
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 12 19
Ester Formation
Acetic anhydride with pyridine catalyst converts all the oxygens to acetate esters.
Chapter 23 20
Osazone FormationBoth C1 and C2 react with phenylhydrazine.
Chapter 12 21
Kiliani-Fischer Synthesis• This process lengthens the aldose chain.• A mixture of C2 epimers is formed.
Chapter 12 22
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 23
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 24
Cellobiose• Two glucose units linked 1-4’.• Disaccharide of cellulose.• A mutarotating, reducing sugar.
Chapter 12 25
MaltoseTwo glucose units linked 1-4’.
Chapter 12 26
Lactose• Galactose + glucose linked 1-4’.• “Milk sugar.”
Chapter 12 27
Sucrose• Glucose + fructose, linked 1-1’• Nonreducing sugar
Chapter 12 28
Cellulose
• Polymer of D-glucose, found in plants.• Mammals lack the -glycosidase enzyme.
Chapter 12 29
Amylose• Soluble starch, polymer of D-glucose.• Starch-iodide complex, deep blue.
Chapter 12 30
AmylopectinBranched, insoluble fraction of starch.
Chapter 12 31
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.
REVIEW
In the Fischer projection of D-(+)-glyceraldehyde, the hydroxyl group on the asymmetric carbon center is:
A) on the bottomB) on the topC) at the leftD) at the rightE) present as a hemiacetal
In the Fischer projection of D-(+)-glyceraldehyde, the hydroxyl group on the asymmetric carbon center is:
A) on the bottomB) on the topC) at the leftD) at the rightE) present as a hemiacetal
All naturally occurring sugars can be degraded to:
A) D-(-)-glyceraldehydeB) D-(+)-glyceraldehydeC) L-(-)-glyceraldehydeD) L-(+)-glyceraldehydeE) none of the above
All naturally occurring sugars can be degraded to:
A) D-(-)-glyceraldehydeB) D-(+)-glyceraldehydeC) L-(-)-glyceraldehydeD) L-(+)-glyceraldehydeE) none of the above
All chiral D-sugars rotate plane-polarized light:
A) clockwise.B) counterclockwise.C) +20.0°.D) in a direction that cannot be predicted but
must be determined experimentally.E) since they are optically inactive.
All chiral D-sugars rotate plane-polarized light:
A) clockwise.B) counterclockwise.C) +20.0°.D) in a direction that cannot be predicted but
must be determined experimentally.E) since they are optically inactive.
The structure of D-arabinose is shown below. Which of the following correctly describes the configurations of the asymmetric carbons in D-arabinose?
A) 2S, 3R, 4RB) 2R, 3S, 4SC) 2S, 3R, 4SD) 2R, 3S, 4RE) 2S, 3S, 4R
The structure of D-arabinose is shown below. Which of the following correctly describes the configurations of the asymmetric carbons in D-arabinose?
A) 2S, 3R, 4RB) 2R, 3S, 4SC) 2S, 3R, 4SD) 2R, 3S, 4RE) 2S, 3S, 4R
Stereoisomeric aldohexoses that differ in configuration at only a single carbon are:
A) meso compounds.B) threo sugars.C) enantiomers.D) constitutional isomers.E) epimers.
Stereoisomeric aldohexoses that differ in configuration at only a single carbon are:
A) meso compounds.B) threo sugars.C) enantiomers.D) constitutional isomers.E) epimers.
Draw the Haworth structure of β-D-glucopyranose.
Draw the Haworth structure of β-D-glucopyranose.
Answer:
Anomers of D-glucopyranose differ in their stereochemistry at:
A) C5B) C4C) C3D) C2E) C1
Anomers of D-glucopyranose differ in their stereochemistry at:
A) C5B) C4C) C3D) C2E) C1
The α and β anomers of a D-glucopyranose are related as:
A) enantiomers.B) meso compounds.C) structural isomers.D) epimers.E) disaccharides.
The α and β anomers of a D-glucopyranose are related as:
A) enantiomers.B) meso compounds.C) structural isomers.D) epimers.E) disaccharides.
Name .
a.-D-Fructopyranoseb.-D-Fructopyranosec.-D-Fructofuranosed.-D-Fructofuranose
O
CH2OH
OH
OH
OH
CH2OH
a.-D-Fructopyranoseb.-D-Fructopyranosec.-D-Fructofuranosed.-D-Fructofuranose
The cyclic structure comes from D-fructose and has a five-membered ring (furan). The OH on the far-right carbon is pointed down ().
List the aldose carbon(s) that are oxidized with HNO3.
a. The first carbonb.The second carbonc. The last carbond.The second to the last carbone.The first and last carbon
a. The first carbonb. The second carbonc. The last carbond. The second to the last carbone. The first and last carbon
Nitric acid oxidizes an aldehyde and –CH2OH.
List the aldose carbon(s) that are oxidized with Tollens reagent.
a. The first carbonb.The second carbonc. The last carbond.The second to the last carbone.The first and last carbon
a.The first carbonb.The second carbonc. The last carbond.The second to the last carbone.The first and last carbon
Tollens reagent oxidizes an aldehyde.
List the sugar hydroxyl(s) that are methylated with CH3I and AgI.
a. On Carbon 1b.On Carbon 2c. On CH2OHs only
d.On all carbonse.None of them
a. On Carbon 1b.On Carbon 2c. On CH2OHs only
d.On all carbonse.None of them
CH3I and AgI methylate all hydroxyl groups.
List the sugar hydroxyl(s) that are esterified with anhydrides.
a. On Carbon 1b.On Carbon 2c. On CH2OHs only
d.On all carbonse.None of them
a. On Carbon 1b.On Carbon 2c. On CH2OHs only
d.On all carbonse.None of them
All hydroxyl groups are esterified.
Explain what happens in the Ruff degradation.
a. The aldose chain is shortened by one carbon.b.The aldose chain is lengthened by one carbon.c. Two aldose chains combine.d.Branching occurs on the aldose chain.
a.The aldose chain is shortened by one carbon.b.The aldose chain is lengthened by one carbon.c. Two aldose chains combine.d.Branching occurs on the aldose chain.
The Ruff degradation shortens the aldose chain by one carbon.
Explain what happens in the Kiliani–Fischer synthesis.
a. The aldose chain is shortened by one carbon.b.The aldose chain is lengthened by one carbon.c. Two aldose chains combine.d.Branching occurs on the aldose chain.
a. The aldose chain is shortened by one carbon.b.The aldose chain is lengthened by one
carbon.c. Two aldose chains combine.d.Branching occurs on the aldose chain.
The Kiliani–Fischer synthesis lengthens the aldose chain by one carbon.
Describe amylose.
a.-1,4’ Glycosidic linkagesb. Water solublec. Polymer of -D-glucopyranosed. All of the abovee. None of the above
a.-1,4’ Glycosidic linkagesb. Water solublec. Polymer of -D-glucopyranosed. All of the abovee. None of the above
65
End of Chapter 12