General

Organic Chemistry
Two credits
Second Semester 2009

King Saud bin Abdulaziz University for Health Science

Reference Book: Organic Chemistry: A Brief Course,

by Robert C. Atkins and Francis A. Carey
Third Edition

Instructor: Rabih O. Al-Kaysi, PhD.

 Lecture 24

Chapter 15

Carbohydrates
Classification of Carbohydrates
Classification of Carbohydrates

monosaccharide
disaccharide
oligosaccharide
polysaccharide
 Monosaccharide

is not cleaved to a simpler carbohydrate on

hydrolysis
glucose, for example, is a monosaccharide
 Disaccharide

is cleaved to two monosaccharides on hydrolysis

these two monosaccharides may be the
same or different

C12H22O11 + H2O

sucrose
(a disaccharide)
 Disaccharide

is cleaved to two monosaccharides on hydrolysis

these two monosaccharides may be the
same or different

C12H22O11 + H2O C6H12O6 + C6H12O6

glucose
sucrose (a monosaccharide)
fructose
(a disaccharide)
(a monosaccharide)
 Higher Saccharides

oligosaccharide:
gives three or more monosaccharide units on
hydrolysis
polysaccharide:
yields more than 10 monosaccharide units
 Some Classes of Carbohydrates

No. of carbons Aldose Ketose

4 Aldotetrose Ketotetrose
5 Aldopentose Ketopentose
6 Aldohexose Ketopentose
7 Aldoheptose Ketoheptose
8 Aldooctose Ketooctose

Just for general knowledge, will not be tested on

Fischer Projections and D-L Notation
Fischer Projections
Fischer Projections
Fischer Projections of Enantiomers
Fischer Projections of Enantiomers
 Enantiomers of Glyceraldehyde

CH O CH O

H OH HO H
D L

CH2OH CH2OH

(+)-Glyceraldehyde (–)-Glyceraldehyde
The Aldotetroses
 An Aldotetrose

1 CH O
2
H OH
3
H OH

4
CH2OH

stereochemistry assigned on basis of whether

configuration of highest-numbered stereogenic center
is analogous to D or L-glyceraldehyde
Just for general knowledge, will not be tested on
 An Aldotetrose

1 CH O
2
H OH
3
H OH
D 4
CH2OH

stereochemistry assigned on basis of whether

configuration of highest-numbered stereogenic center
is analogous to D or L-glyceraldehyde
Just for general knowledge, will not be tested on
 An Aldotetrose

1 CH O
2
H OH
3
H OH

4
CH2OH

D-Erythrose

Just for general knowledge, will not be tested on

 The Four Aldotetroses

CH O CH O CH O CH O

H OH HO H HO H H OH

H OH HO H H OHHO H

CH2OH CH2OH CH2OH CH2OH

D-Erythrose L-Erythrose D-Threose L-Threose

Just for general knowledge, will not be tested on

Aldopentoses and Aldohexoses
 The Aldopentoses

There are 8 aldopentoses.

Four belong to the D-series; four belong to
the L-series.
Their names are ribose, arabinose, xylose,
and lyxose.
 The Four D-Aldopentoses

CH O CH O CH O CH O

H OH HO H H OH HO H
H OH H OH HO H HO H
H OH H OH H OH H OH

CH2OH CH2OH CH2OH CH2OH

D-Ribose D-Arabinose D-Xylose D-Lyxose

Just for general knowledge, will not be tested on
 Aldohexoses

There are 16 aldopentoses.

8 belong to the D-series; 8 belong to the L-
series.
Their names and configurations are best
remembered with the aid of the mnemonic
described in Section 25.5.
 L-Aldohexoses

There are 8 CH O CH O
aldohexoses of
the L-series. H OH HO H
They have the HO H H OH
same name as
H OH HO H
their mirror image
except the prefix is H OH HO H
L- rather than D-.
CH2OH CH2OH

D-(+)-Glucose L-(–)-Glucose
Just for general knowledge, will not be tested on
Cyclic Forms of Carbohydrates:
Furanose Forms
 Recall

R R
•• ••
C O •• + R"OH R"O C O H
•• •• ••
R' R'
Product is a hemiacetal.
 Carbohydrates Form Cyclic Hemiacetals

1 CH O
2 OH
O
4 1
3
3 2 H
4
CH2OH
equilibrium lies far to the right
cyclic hemiacetals that have 5-membered rings
are called furanose forms
 D-Erythrose

1 CH O
2 HH H
H OH OH
O
4 1
3
H OH 3 2 H
H
4 OH OH
CH2OH

stereochemistry is maintained during cyclic

hemiacetal formation
 D-Ribose

1
CH O
2
H OH
3
H OH
4
H OH

5 CH OH
2 2

furanose ring formation involves OH group at C-4

 D-Ribose

1
CH O
5
2
H OH H CH2OH 1
3
OH H H CH O
H 4
4
H OH HO 3 2
OH OH
5 CH OH
2 2

need C(3)-C(4) bond rotation to put OH in proper

orientation to close 5-membered ring

Just for general knowledge, will not be tested on

 D-Ribose

5 5
HOCH2 OH H CH2OH 1
1
4 H H CH O 4 H H CH O

H 3 2 HO 3 2
OH OH OH OH

Just for general knowledge, will not be tested on

 D-Ribose

5
HOCH2 OH
1
4 H H CH O

H 3 2

OH OH

CH2OH group becomes a substituent on ring

Just for general knowledge, will not be tested on

 D-Ribose

5
5
HOCH2 OH HOCH2
1
H O H OH
4 H H CH O
4 1

H 3 2 3 2 H
H
OH OH OH OH

-D-Ribofuranose
CH2OH group becomes a substituent on ring
Cyclic Forms of Carbohydrates:
Pyranose Forms
 Carbohydrates Form Cyclic Hemiacetals

1
CH O
2 5
O OH
3 4 1
4
3 2 H
5 CH2OH

cyclic hemiacetals that have 6-membered rings

are called pyranose forms
 D-Ribose

1
CH O
2
H OH
3
H OH
4
H OH

5 CH2OH

pyranose ring formation involves OH group at C-5

Just for general knowledge, will not be tested on

 D-Ribose

1
CH O 5
H CH2OH
2 1
H OH H
4 H CH O
3
H OH
H
4
OH HO 3 2
OH OH
5 CH2OH

pyranose ring formation involves OH group at C-5

Just for general knowledge, will not be tested on

 D-Ribose

5
H CH2OH
1
4 H H CH O

HO 3 2
OH OH

pyranose ring formation involves OH group at C-5

Just for general knowledge, will not be tested on

 D-Ribose

H 5
5 H CH2OH
H O OH 1
4 H 1 4 H H CH O
H H
HO 3 2 H HO 3 2
OH OH OH OH

-D-Ribopyranose

Just for general knowledge, will not be tested on

 D-Glucose

1
CH O
2
H OH
3
HO H
4
H OH
5
H OH
6
CH2OH

pyranose ring formation involves OH group at C-5

 D-Glucose

6
6 HOCH2
HOCH2 OH
5
H 5 H O OH
H 4 H 1
4
OH CH O OH H
H 1
3 2 HO 3 2 H
HO
H OH
H OH

-D-Glucopyranose

Just for general knowledge, will not be tested on

 D-Glucose

6 6
HOCH2 HOCH2
5 5
H O H H O OH
4 H 1 4 H 1
OH H OH H
HO 3 2 OH HO 3 2 H
H OH H OH

-D-Glucopyranose -D-Glucopyranose

Just for general knowledge, will not be tested on

 D-Glucose

H H
HOCH2 H HOCH2 H
HO O HO O
HO OH HO H
1 1
H OH H OH
H H H OH

-D-Glucopyranose -D-Glucopyranose

OH group at anomeric carbon is axial

in -D-glucopyranose
Just for general knowledge, will not be tested on
Ketoses
 Ketoses

Ketoses are carbohydrates that have a ketone

carbonyl group in their open-chain form.
C-2 is usually the carbonyl carbon.
 Examples

CH2OH CH2OH CH2OH

O O O
H OH H OH HO H
H OH HO H H OH
H OH
CH2OH CH2OH
CH2OH
D-Ribulose L-Xyulose D-Fructose
Deoxy Sugars
 Deoxy Sugars

Often one or more of the carbons of a

carbohydrate will lack an oxygen substituent.
Such compounds are called deoxy sugars.
 Examples

CH O CH O

H H H OH
H OH H OH
H OH HO H

CH2OH HO H

CH3
2-Deoxy-D-ribose 6-Deoxy-L-mannose
Amino Sugars
 Amino Sugars

An amino sugar has one or more of its oxygens

replaced by nitrogen.
 Example

HOCH2
HO O
HO OH
NH

O C

CH3

N-Acetyl-D-glucosamine
 Example

OH

H3C O

NH2
HO

L-Daunosamine
Branched-Chain Carbohydrates
 Branched-Chain Carbohydrates

Carbohydrates that don't have a continuous

chain of carbon-carbon bonds are called
branched-chain carbohydrates.
 Examples

CH O
OH
CH3
H OH
H3C O
HO CH2OH
NH2
HO
CH2OH

D-Apiose L-Vancosamine
Glycosides
 Glycosides

Glycosides have a substituent other than OH at

the anomeric carbon.
Usually the atom connected to the anomeric
carbon is oxygen.
 Example
HOCH2
HO O
HO OH
OH
D-Glucose

Linamarin is an HOCH2
O-glycoside O CH3
HO
derived from
HO OCC N
D-glucose.
OH CH3
Disaccharides
 Disaccharides

Disaccharides are glycosides.

The glycosidic linkage connects two
monosaccharides.
Two structurally related disaccharides are
cellobiose and maltose. Both are derived
from glucose.
 Maltose and Cellobiose
HOCH2 HOCH2
O  O
HO 1 O 4 OH Maltose

HO OH HO OH
Maltose is composed of two glucose units linked
together by a glycosidic bond between C-1 of
one glucose and C-4 of the other.
The stereochemistry at the anomeric carbon of
the glycosidic linkage is .
The glycosidic linkage is described as (1,4)
 Maltose and Cellobiose
HOCH2 HOCH2
O  O
HO 1 O 4 OH Cellobiose

HO OH HO OH
Cellobiose is a stereoisomer of maltose.
The only difference between the two is that
cellobiose has a (1,4) glycosidic bond while
that of maltose is (1,4).
 Maltose and Cellobiose

Maltose Cellobios
e
Just for general knowledge, will not be tested on
 Cellobiose and Lactose
HOCH2 HOCH2
O  O
HO 1 O 4 OH Cellobiose

HO OH HO OH
Cellobiose and lactose are stereoisomeric
disaccharides.
Both have (1,4) glycosidic bonds.
The glycosidic bond unites two glucose units in
cellobiose. It unites galactose and glucose in
lactose.
 Cellobiose and Lactose
HOCH2 HOCH2
O  O
HO 1 O 4 OH Lactose

HO OH HO OH
Cellobiose and lactose are stereoisomeric
disaccharides.
Both have (1,4) glycosidic bonds.
The glycosidic bond unites two glucose units in
cellobiose. It unites galactose and glucose in
lactose.
Polysaccharides
 Cellulose

Cellulose is a polysaccharide composed of

several thousand D-glucose units joined by
(1,4)-glycosidic linkages. Thus, it can also
be viewed as a repeating collection of
cellobiose units.
 Cellulose

Four glucose units of a cellulose chain.

 Starch

Starch is a mixture of amylose and amylopectin.

Amylose is a polysaccharide composed of 100 to
several thousand D-glucose units joined by
(1,4)-glycosidic linkages.