Biomolecules:

CARBOHYDRATES
• Interconvert Haworth, Fischer, and chair representations of
monosaccharides.
• Construct furanose and pyranose Haworth projections of
monosaccharides.
• Classify monosaccharides as:
a) ketoses or aldoses
b) L-sugars or D-sugars
c) Alpha- or Beta-anomers
• d) Outline the mechanism of condensation and
hydrolysis of carbohydrates
• Use chemical equations to describe the equilibrium
process associated with mutarotation.
• Illustrate the reactions responsible for the positive
results in the different tests for carbohydrates.
• Predict whether a carbohydrate is reducing or non-
reducing based on its structure.
• Interpret results of the different tests for
carbohydrates.
 Carbohydrate Synthesis and Metabolism

• Carbohydrates are storehouses of chemical energy.

• They are synthesized by green plants and algae by
photosynthesis, a process that uses the energy from the sun to
convert carbon dioxide and water into glucose and oxygen.
• This energy is released when glucose is metabolized.
• The oxidation of glucose is a multistep process that forms carbon
dioxide, water, and a great deal of energy.

4
 Diversity of Carbohydrates

• Carbohydrates, commonly referred to as sugars and starches, are polyhydroxy

aldehydes and ketones, or compounds that can be hydrolyzed to them.

5
 Monosaccharides

• The simplest carbohydrates are called monosaccharides or simple

sugars.
• They have three to seven carbon atoms in a chain, with a carbonyl group
at either the terminal carbon (C1) or the carbon adjacent to it (C2).
• In most carbohydrates, each of the remaining carbon atoms has a
hydroxy group.
• Monosaccharides are usually drawn vertically, with the carbonyl group at
the top.

6
 Common Names of Monosaccharides
• All carbohydrates have common names.
• The simplest aldehyde is glyceraldehyde, and the simplest ketone is
dihydroxyacetone.
• They are the only monosaccharides whose names do not end in the
suffix “-ose.”

7
 Naming Monosaccharides

• A monosaccharide is called:

• These terms are then combined with the words aldose and ketose
to indicate both the number of carbon atoms in the
monosaccharide, and whether it contains an aldehyde or ketone
functionality.
• Thus, glyceraldehyde is an aldotriose, glucose is an aldohexose,
and fructose is a ketohexose.
8
 Stereocenters in Glyceraldehyde

• All carbohydrates except for dihydroxyacetone contain one or

more stereogenic centers.
• The simplest aldehyde, glyceraldehyde, has one stereogenic
center, so there are two possible enantiomers.
• Only the enantiomer with the R configuration occurs naturally.

9
 Fischer Projections

• The stereogenic centers in sugars are often depicted following a

different convention than is usually seen for other stereogenic
centers.

• Instead of drawing a tetrahedron with two bonds in the plane, one

in front of the plane and one behind it, the tetrahedron is tipped so
that horizontal bonds come forward (drawn on wedges) and
vertical bonds go behind (on dashed lines).

• This structure is then abbreviated by a cross formula, also called

a Fischer projection formula.

10
 Rules for Fischer Projections

• You should not rotate a Fischer projection formula in the plane of

the page, since you may inadvertently convert a compound into its
enantiomer.
11
 Number of Stereoisomers

• The number of possible stereoisomers of a monosaccharide

increases exponentially with the number of stereogenic centers
present.
• An aldohexose has four stereogenic centers, and so it has
24 = 16 possible stereoisomers, or eight pairs of enantiomers.

12
 Fischer Projections with Multiple Stereocenters

• Fischer projection formulas are also used for compounds like

aldohexoses that contain several stereogenic centers.
• In this case, the molecule is drawn with a vertical carbon skeleton
and the stereogenic centers are stacked one above another.
• Using this convention, all horizontal bonds project forward (on
wedges).

13
 Caution with Fischer Projections

• Although Fischer projections are commonly used to depict monosaccharides with

many stereogenic centers, care must be exercised in using them since they do
not give a true picture of the 3-D structures they represent.
• Since each stereogenic center is drawn in the less stable eclipsed conformation,
• the Fischer projection of glucose really represents the molecule in a
cylindrical conformation.

Figure 28.2
A Fischer projection and the
3-D structure of glucose

14
 Naming D- and L- Isomers of Monosaccharides

• Although the prefixes R and S can be used to designate the configuration of

stereogenic centers in monosaccharides, an older system of nomenclature uses
the prefixes D- and L- instead.
• Naturally occurring glyceraldehyde with the R configuration is called the D-
isomer.
• Its enantiomer, (S)-glyceraldehyde, is called the L-isomer.

15
 Assigning RS Configurations to
Fischer Projections
• R,S designations can be assigned to any stereogenic center
drawn as a Fischer projection formula in the following manner:
• [1] Assign priorities (1 → 4) to the four groups bonded to the
stereogenic center using the rules detailed in Section 5.6.
• [2] When the lowest priority group occupies a vertical bond—that
is, it projects behind the plane on a dashed line—tracing a circle in
the clockwise direction gives the R configuration. Tracing a circle
in the counterclockwise direction gives the S configuration.
• [3] When the lowest priority group occupies a horizontal bond—
that is, it projects in front of the plane on a wedge—reverse the
answer obtained in Step [2] to designate the configuration.

16
 Naming D- and L- Isomers of Monosaccharides

• The letters D and L are used to label all monosaccharides, even

those with multiple stereogenic centers.
• The configuration of the stereogenic center furthest from the
carbonyl group determines whether the monosaccharide is D- or
L-.

17
 D and L vs. d and l

• Note that the two designations (D and L vs. d and l) refer to very
different phenomena:

• D and L designates the configuration around a stereogenic

center.

• d and l refers to the direction in which plane polarized light is

rotated.

• There is no correlation between these two designations.

18
 D- and L- Glucose

• Glucose and all other naturally occurring sugars are

D-sugars.
• L-Glucose, a compound that does not occur in nature, is the
enantiomer of D-glucose.
• L-Glucose has the opposite configuration at every stereogenic
center.

19
 D-Aldotetroses

• Beginning with D-glyceraldehyde, one may formulate other D-aldoses

having four, five, or six carbon atoms by adding carbon atoms (each
bonded to H and OH), one at a time, between C1 and C2.
• Two D-aldotetroses can be formed from D-glyceraldehyde, one with the
new OH group on the right and one with the new OH group on the left.
• Their names are D-erythrose and D-threose:

20
 Stereoisomers of D-Aldotetroses

• Since each aldotetrose has two stereogenic centers, there are 22

or four possible stereoisomers.
• D-erythrose and D-threose are two of them.
• The other two are their enantiomers—L-erythrose and
L-threose, respectively.

Figure 28.3
The four stereoisomeric
aldotetroses

21
The Family of D-Aldoses

22
 The Family of D-Aldoses

• D-Ribose, D-arabinose, and D-xylose are all common aldopentoses in nature.

• Of the D-aldohexoses, only D-glucose and D-galactose are common in nature.
• D-Glucose is by far the most abundant of all D-aldoses.
• D-Glucose comes from the hydrolysis of starch and cellulose, and D-galactose
comes from the hydrolysis of fruit pectins.
• Diastereomers that differ in the configuration around one stereogenic center only
are called epimers.

23
 The Family of D-Ketoses

Figure 28.5

24
 Physical Properties of Monosaccharides

• They are all sweet tasting, but their relative sweetness varies a
great deal.

• They are polar compounds with high melting points.

• The presence of so many polar functional groups capable of

hydrogen bonding makes them water soluble.

• Unlike most other organic compounds, monosaccharides are so

polar that they are insoluble in organic solvents like diethyl ether.

25
 Cyclic Forms of Monosaccharides

• The hydroxy and carbonyl groups of monosaccharides can undergo

intramolecular cyclization to form hemiacetals having either five or six
atoms in the ring.

26
 Cyclization of pyranoses

• Cyclization of a hydroxy carbonyl compound always forms a

stereogenic center at the hemiacetal carbon, called the anomeric
carbon.

• Cyclization forms the more stable ring size in a given molecule.

• The most common monosaccharides, the aldohexoses like
glucose, typically form a pyranose ring.
27
 Cyclizing Glucose

• Cyclization of the open chain form of glucose follows the general rules:
• The O atom on the stereogenic center (C5) is in the proper position
for cyclization to form a pyranose ring.
• This O is the sixth atom from the carbonyl carbon and upon closure
forms the favorable six-membered ring.

28
 D-Aldotetroses

• To translate the acyclic form of glucose into a cyclic hemiacetal, we must

draw the hydroxy aldehyde in a way that suggests the position of the
atoms in the new ring, and then draw the ring.
• By convention the O atom in the new pyranose ring is drawn in the upper
right-hand corner of the six-membered ring.

29
 Anomers of D-Glucose

• Because cyclization creates a new stereogenic center, there are

two cyclic forms of D-glucose, an  anomer and a  anomer.
• All the original stereogenic centers maintain their configuration in
both of the products formed.

30
 Haworth Projections

• These flat six-membered rings used to represent the cyclic

hemiacetals of glucose and other sugars are called Haworth
projections.
• -D-Glucose and -D-glucose are diastereomers because only the
anomeric carbon has a different configuration.
• The cyclic forms of glucose now have five stereogenic centers—
the four from the starting hydroxy aldehyde and the new anomeric
carbon.
• The  anomer has the anomeric OH group and the CH2OH group
trans.
• The  anomer has the anomeric OH group and the CH2OH group
cis.

31
 Three Forms of Glucose

• The acyclic aldehyde and two cyclic hemiacetals are all in equilibrium.
• Each cyclic hemiacetal can be isolated and crystallized separately, but
when one compound is placed in solution, an equilibrium mixture of all
three forms results.
• This process is called mutarotation.
• The relative amounts of each species at equilibrium are shown below.

Figure 28.6

32
 Three Forms of Glucose

Figure 28.6

33
34
35
Convert a Haworth Projection to a Chair Form

36
 Furanose Rings
• Certain monosaccharides—notably aldopentoses and
ketohexoses—form furanose rings, not pyranose rings, in
solution.

37
 Drawing Furanose Forms

• The same procedure can be used to draw the furanose form of D-

fructose, the most common ketohexose.
• Because the carbonyl group is at C2 (instead of C1, as in aldoses), the
OH group at C5 reacts to form the hemiacetal in the five-membered ring.
• Two anomers are formed.

38
 PRACTICE PROBLEM

Convert the Fischer projections of the following sugars to furanose/pyranose

Haworth and chair (for pyranose) projections:
 CONCEPT CHECK

Convert the Fischer projections of the following sugars to furanose/pyranose

Haworth and chair (for pyranose) projections:

D- Idose
D- Gulose
Condensation and Hydrolysis of
Carbohydrates
 Types of Carbohydrates

Carbohydrates are synthesized by photosynthesis

in plants
• Grains, cereals, bread, sugar cane
Glucose is major energy source
• A gram of digested carbohydrate gives about 4 kcal
of energy
• Complex carbohydrates are best for diet
• USDA recommends about 45-65% daily calories from
carbohydrates
 Biological Monosaccharides

Glucose is the most important sugar in the human body

• Found in many foods
• Many common names: dextrose and blood sugar
• Its concentration in the blood is regulated by insulin and
glucagon
Under physiological conditions, glucose exists in a cyclic
hemiacetal form where the C-5 hydroxyl reacts with the C-1
carbonyl group
• Two isomers are formed which differ in the location of the -OH on
the acetal carbon, C-1
An aldohexose with molecular formula C6H12O6
 Basic Carbohydrate Types

Monosaccharides
• e.g., glucose, fructose
• One sugar (saccharide) molecule
Disaccharides
• e.g., sucrose, lactose
• Two monosaccharides linked together
• Linkage is called a glycosidic bond
Oligosaccharides
• Three to ten monosaccharides linked by glycosidic bonds
Polysaccharides
• e.g., starch, glycogen, cellulose
• Chains of linked monosaccharide units
 Monosaccharides

Monosaccharides are composed of:

• Carbon
• Hydrogen
• Oxygen
• Basic Formula = (CH2O)n n = any integer 3 – 7
Many monosaccharides also contain chemical
modifications
• Amino groups
• Phosphate groups
 PRACTICE PROBLEM

Classify each of the following sugars.

1. 3.

2. 4.
 Benedict’s Reagent
The aldehyde groups of aldoses are oxidized by Benedict’s
reagent, an alkaline Cu2+ solution
The blue color of the reagent fades as reaction occurs
reducing Cu2+ to Cu+ with a red-orange precipitate forming
as Cu2O results
Test can measure glucose in urine
 Reducing Sugars

All monosaccharides and the disaccharides except sucrose

are reducing sugars
Ketoses can isomerize to aldoses via enediol reaction
 Biologically Important Disaccharides

The anomeric -OH can react with another -OH on

an alcohol or sugar, forming a glycosidic bond
Water is lost to form an acetal
Glycosidic Bond Formed in Sucrose
 Polysaccharides

Homopolysaccharides – composed of one type of

monosaccharide
Heteropolysaccharides – made up of two or more different
monosaccharides
Starch
• Storage polymers of α linked glucose found in plants
• If the links are:
• Only 1,4 links, the polymer is linear = amylose
• Amylose usually assumes a helical configuration with six glucose units per turn
• Comprises about 80% of plant starch
• Both 1,4 and 1,6 links then, the polymer structure is branched = amylopectin
• Highly branched with branches of approximately 20-25 glucose units