Organic Chemistry

Lecture 8: Carbohydrates

1
 Introduction

Carbohydrates:
• commonly referred to as sugars, abundant in nature
• polyhydroxy aldehydes or ketones
• For energy storage, building blocks for structure rigidity

Naturally occurring from photosynthesis

2
 Classifications

o Monosaccharides contain a single polyhydroxy aldehyde or ketone unit

(saccharo is Greek for “sugar”)
i.e. glucose, fructose

o Disaccharides consist of two monosaccharide units linked together by a

covalent bond
i.e. sucrose

o Oligosaccharides contain from 3 to 10 monosaccharide units

i.e. raffinose

o Polysaccharides contain very long chains of hundreds or thousands of

monosaccharide units, which may be either in straight or branched chains
i.e. cellulose, glycogen, starch.

3
 Classifications

I
I
I
I
monosaccharide disaccharide
:
I M
:::::
-

-------------------L------------------------------
M
:::::
<l)
u
N
....-<
0
N

oligosaccharide polysaccharide
-
g.
(chain containing (long chain with possibly hundreds u
3-10 units) or thousands of units)

4
 Monosaccharides

Aldoses vs. Ketoses

1. aldo or keto: aldehyde or ketone

2. tri-, tetr-, pent-, hex-, or hept-: the number of carbon atoms
3. –ose: indicating a carbohydrate

5
 Monosaccharides

Glyceraldehyde: smallest carbohydrate

mirror

L-glyceraldehyde D-glyceraldehyde

“L”: -OH group (or another functional group) is on the left of the chiral carbon
“D”: -OH is on the right of the chiral carbon.
Note: the carbonyl (C=O) group is at the top.
6
 Monosaccharides

D and L Sugars D Sugar will be degraded to D-Glyceraldehyde

• Most of natural carbohydrates

are D sugars
• L sugar is the enantiomer of
the corresponding D sugar
• D/L does NOT indicate
dextrorotatory (+) or
levororatory (-)
7
 Practice- Group Work
This is your HW. 1pt each.
1. Classify each of the following carbohydrates as an
aldose or ketose and then insert the appropriate term
to indicate the number of carbon atoms present (e.g.,
an aldopentose):
2. Would you expect an aldohexose and a ketohexose to be
constitutionally isomeric? Explain why or why not.
3. Determine whether each of the
following carbohydrates is a D sugar or an
L sugar and assign a configuration for each
chiral center.
After assigning the configuration for all
of the chiral centers, do you notice any
trend that would enable you to assign
the configuration of a chiral center in a
carbohydrate more quickly?
10
 Practice- Group Work

4. D-allose is an aldohexose in which all four chiral centers have the R configuration. Draw a
Fischer projection of each of the following compounds:
(a) D-Allose (b) L-Allose

5. There are only two stereoisomeric ketotetroses.

(a) Draw both of them.
(b) Identify their stereoisomeric relationship.
(c) Identify which is a D sugar and which is an l sugar.

6. There are four stereoisomeric aldotetroses.

(a) Draw all four and arrange them in pairs of enantiomers.
(b) Identify which stereoisomers are d sugars and which are l sugars.

10
 Cyclic Structures of Monosaccharides

Aldehyde + alcohol -> a hemiacetal (w/ acid catalyst)

hemiacetal C

11
 Cyclic Structures of Monosaccharides

Aldehyde + alcohol -> a hemiacetal (w/ acid catalyst)

hemiacetal C
Important: keep track of all carbon atoms

13
 Practice- Group Work

7. Draw the cyclic hemiacetal that is formed when each of the following bifunctional
compounds is treated with aqueous acid: (0.5 each)

8. Identify the hydroxyaldehyde that will cyclize under acidic conditions to give the
following hemiacetal: (1 pt)

14
 Pyranose Forms of Monosaccharides

D-Glucose D-glucopyranose mixture

Pyranose ring
a six-membered sugar
ring system containing
an O atom.
15
 Practice- Group Work

Draw the Haworth projection of α-D-galactopyranose.

• Always start with a pyranose

• “D” :CH2OH group must be in the up position. Why? (1pt)

• Any OH on the right -> pointing down

• Any OH on the left -> pointing up
Why? (1pt) 18
 Practice

9. Draw a Haworth projection for each of the following compounds: (0.5 each)
(a) β-D-Galactopyranose (b) α-D-Mannopyranose (c) α-D-Allopyranose
(d) β-D-Mannopyranose (e) β-D-Glucopyranose (f) α-D-Glucopyranose

1
Three-Dimensional Representations of Pyranose

Ring
flip?
(1pt)

2
Furanose Forms of Monosaccharides

Furanose
a five-membered sugar ring
system containing an O atom.

20
 Furanose Forms of Monosaccharides

D-Fructose can cyclize to give furanose or pyranose

21
 Practice

10. (0.5pt each) Consider the structures of the following two D-aldotetroses:

Each of these compounds exists as a furanose ring, which is formed when the OH
at C4 attacks the aldehyde group. Draw each of the following furanose rings:
(a) α-D-Erythrofuranose (b) β-D-Erythrofuranose
(c) α-D-Threofuranose (d) β-D-Threofuranose

22
 Important Monosaccharides

Ribose and Deoxyribose

Two pentoses, ribose and deoxyribose, are extremely important because

they are used in the synthesis of nucleic acids (DNA and RNA), substances
essential in protein synthesis and the transfer of genetic material

23
 Important Monosaccharides

Glucose (sometimes called dextrose)

o Hexose glucose is the most important nutritionally and the most abundant in
nature.
o Glucose is present in honey and fruits such as grapes, figs, and dates
o Also known as blood sugar because it is the sugar transported by the blood to
body tissues to satisfy energy requirements.
o Other sugars absorbed into the body must be converted to glucose by the liver
o Commonly used as a sweetener in confections and other foods

24
 Important Monosaccharides

Galactose
o A hexose with a structure very similar to that of glucose.
o The only difference: the orientation of the hydroxy group attached to carbon 4.
o Like glucose, galactose can exist in , , or open-chain forms
o Synthesized in the mammary glands, where it is incorporated into lactose, the
sugar found in milk.
o Also a component of substances present in nerve tissue

27
 Important Monosaccharides

Diabetes is characterized by an impairment of the body’s ability to

utilize blood glucose

Synthetic noncarbohydrate sweetening agents 28

 Reactions of Monosaccharides

Glycoside Formation

Cyclic monosaccharides (hemiacetals and hemiketals) readily react with

alcohols in the presence of acid to form acetals and ketals.
acetal C

hemiacetal C
glycoside - another name for a carbohydrate containing an acetal
or ketal group.

30
 Reactions of Monosaccharides

Glycoside Formation

31
 Reactions of Monosaccharides

Oxidation

32
 Reactions of Monosaccharides

Oxidation

Reducing sugars give positive tests to these oxidizing agents:

• Tollens’ reagent (Ag+ in aqueous ammonia)
• Fehling’s reagent (Cu2+ in aqueous sodium tartrate)
• Benedict’s reagent (Cu2+ in aqueous sodium citrate)
-> chemical test for presence of aldose or ketoses vs. glycoside

Ketose doesn’t undergo oxidation but ketose can isomerized into aldose

Ketose and aldose : reducing sugars

Acetal C
Determine reducing sugar? -> not reducing sugar

33
 Practice
11. Determine whether each of the following compounds is a reducing sugar (0.5 each):

12. When α-D-galactopyranose is treated with ethanol in the presence of an

acid catalyst, such as HCl, two products are formed. Draw both products (1pt)

35
 Disaccharide

o Disaccharides are sugars composed of two monosaccharide units linked together

by the acetal or ketal linkages described earlier.

o They can be hydrolyzed to yield their monosaccharide building blocks by boiling

with dilute acid or reacting them with appropriate enzymes.

o Nutritionally, the most important members of this group are maltose, lactose, and
sucrose.

36
 Disaccharide

Maltose

o Found in germinating grain, is formed during the digestion (hydrolysis) of starch

to glucose.
o Its name is derived from the fact that during the germinating (or malting) of barley,
starch is hydrolyzed, and the disaccharide is formed

o Hydrolysis

37
 Disaccharide

• Lactose

o Lactose, or milk sugar, constitutes 5% of cow’s milk and 7% of human milk by

weight
o Pure lactose is obtained from whey, the watery byproduct of cheese production.
o Lactose is composed of one molecule of D-galactose and one of D-glucose.
o The linkage between the two sugar units is (1→4)

39
 Side story: Lactose Intolerance

https://www.youtube.com/watch?v=G1NGzycaQV0

40
 Disaccharide

Sucrose
o The disaccharide sucrose, common household sugar, is extremely abundant in
the plant world.
o Occurs in many fruits, in the nectar of flowers and in the juices of many plants,
especially sugar cane and sugar beets, the commercial sources.
o Sucrose contains two monosaccharides, glucose and fructose, joined together by
a linkage that is  from carbon 1 of glucose and  from carbon 2 of fructose:

o Hydrolysis

Honeybee has enzyme for this process

-> honey sweeter than table sugar
(fructose sweeter than sucrose)

41
 Polysaccharide

o Not water-soluble (large size)

o Become hydrated individually when exposed to water (due to many –OH groups)
o Some polysaccharides form thick colloidal dispersions when heated in water.
o The polysaccharide known as starch can be used as a thickener in sauces, gravies,
pie fillings, and other food preparations.

42
 Polysaccharide

Starch
o A polymer consisting entirely of D-glucose units.
o The major storage form of D-glucose in plants:
amylose (10–20%) & amylopectin (80–90%)

o Amylose is made up of long unbranched chains of glucose units connected by

(1→4) linkages

43
 Polysaccharide

Starch

Amylose + iodine → deep-blue complex

44
 Polysaccharide

Starch
Amylopectin is not a straight-chain molecule like amylose but contains random
branches
Amylopectin contains as many as 105 glucose units in one gigantic molecule

The partial structure of an amylopectin molecule

45
 Polysaccharide

Glycogen
o Sometimes called animal starch because it is a storage carbohydrate for
animals (analogous to the starch of plants).
o Abundant in the liver and muscles, where excess glucose taken in by an animal
is stored for future use
o On hydrolysis: glycogen forms D-glucose, which helps maintain the normal
blood sugar level and provide the muscles with energy

Each small hexagon represents a

single glucose unit.

46
 Polysaccharide

Cellulose
o The most important structural polysaccharide and is the single most abundant
organic compound on Earth
o Cellulose is a linear polymer consisting of D-glucose units joined by the 1→4
linkage.
o Contains from 300 to 3000 glucose units in one molecule
o Main difference between amylose and cellulose: all the 1 → 4 glycosidic
linkages in cellulose are  instead of 

47
 Polysaccharide

Cellulose

o Humans and other animals lack the necessary enzymes to hydrolyze the 
linkages of cellulose

o Cellulose passes unchanged through the digestive tract and does not contribute
to the caloric value of food

o Animals that use cellulose as a food do so only with the help of bacteria that
possess the necessary enzymes for breakdown

48