Stereochemistry and stereoisomer

Stereochemistry : is the science that deals with structure in three

dimensions .
Isomers : are different compounds that have the same molecular
formula .which are called structural isomers .
Steroisomer : is the particular kind of isomers that are different from each
other only is the way of orientation of atoms is space .
Enantiomers : is the mirror image isomers . These isomers have the same
physical properties except the rotation of the plane polarized light .
They are differ only in the way of orientation of the atoms in space .They
are not superimposable to each other . The non superimposability of
mirror image leads to enantiomer and also gives each of them their
optical activity .
(enantio =opposite ) for example , biochemical compound for leucine
Chiral compound :-
The structural isomers have different physical properties in M.P , b.p.
density
If the isomers have identical properties it must have identical molecular
structure .
It was discovered big number of compounds which contradict this fact
Consider the compound leucine C6H13O2N . this compound present as two
isomers
H3C CH3
CH
CH2
H C CO 2H
Chiral atom NH2
These isomers are differ in taste , the first has bitter taste and the other has
sweat taste because they are different isomers . because they are differ in
orientation of atoms in space
 NH2 CO 2H
CO 2H NH2
H C H C
CH2CH (CH3)2 CH2CH (CH3)2

Two compounds:-three dimensional structure of leucine

Stereoisomer are related in an important way that they are mirror-image of
each other .
Further more these mirror-image are not superimposed .
 NH2 NH2
CO 2H HO 2C
H C C H
CH2CH (CH3)2 (CH3)2CHCH2
Leucine

Mirror-image relationship of the two stereoisomers of lecine .We them

enantiomers
Remember that all objects have a mirror image . However objects can be
superimposed on their mirror image
How we distinguish between chiral and achiral compounds
First we must determined whether this isomers superimposed or not
Chiral compound :- any compound which has one or more carbon atoms
bonded to four different atoms or groups
 Cl
H3C *
CH3 CH2 CH CH3
CH CH CH3
H3C
*
Cl

NH2
CH CO2H
*
The chiral carbon atom is un symmetrical atom . The different between
chirality and optical activity : chirality : objects which are mirror images but
not superimposed , optical activity is a physical property in which the
compound which rotate the plane polarized light .
If the compound composed from two enantiomers i.e. one of them (-) and
the other is (+) the net rotation = zero
A mixture of equal amount of two enantiomers is called racemic mixture , it
is optically inactive
Example
The light-catalyzed butane and chlorination of to form 2-chlorobutane as
one the product .

CH2CH3 CH2CH3
light H H
CH3 CH2 CH2 CH3 + Cl2 C Cl + Cl C
CH3 CH3
2-chloro butane contain chiral carbon but it is inactive because equal
amounts of dextrorotatory and levorotatory isomers are formed in equal
amount.

In living system
The reaction will produce only one of the enantiomers ,the compound will
be optically active and this is the main different between reaction occurs
in lab. and reaction occurs in living system .
Naming of stereoisomers we must mention the specific rotation of
conferbration
Diasteroisomers :-
The compound which contain two or more chiral centers can exist as
more than two sreroisomers . They are not mirror images and not
superimposable .
General rule :- the maximal number of stereoisomers is 2n
n= number of chiral atoms
General rule :- the maximal number of stereoisomers is 2n
n= number of chiral atoms

* *
CH3 CH CH CH CH3
OH OH OH
2 chirals
example of compound containing two chiral centers is the carbohydrate
2,3,4-trihydroxybutyraldehyde

* *
HOCH2 CH CH CHO
OH OH
It has four stereoisomers

CHO CHO
HO C H H C OH
HO C H H C OH
CH2OH CH2OH
I II
-erythroseL -erythroseD

They are pair of enantiomers called Erythose

 CHO CHO
H C OH HO C H
HO C H H C OH
CH2OH CH2OH
III IV
L- thereose D- thereose
These pair of enantiomers called Threose
These pair of enantiomers called Threose
I & II are mirror image and they are not superimposed
III & IV are mirror image and they are not superimposed
( Ι , ΙΙΙ ), ( ΙΙ , Ιv) the compounds are not mirror image (Diastereomers )
and not superimposable
Diastereomers have different physical properties
Ι is liquid
Ιv is solid
Solubility
Erythrose highly soluble in ethanol while Threose slightly soluble in
ethanol
Meso stereoisomers :-
Certain molecules that contain two chiral atoms do not exist as four
stereoisomers .
Specific example is Tartaric acid
 OH
*
HO2C CH CH CO2H
*
OH

CO2H CO2H CO2H CO2H

H C OH HO C H H C OH H
HO C OH
H

HO C H H C OH HOH C OH
H
H C OH
CO2H CO2H CO2H
CO2H

I II III IV
pair of enantiomers identical compound
they are called mesoisomers
 CO2H CO 2H
H C OH rotation 180 HO C H
H C OH HO C H
CO2H CO 2H
III IV

Mesoisomers is optically inactive because they have plane of symmetry. it

superimposed on its mirror image
Resolution of Racemic mixture
Resolution is process of separating of enantiomers into pure stereoisomer
1- mechanical separation :-
it was performed by Pasteur when he crystallize tartaric acid salt he found
two types of crystals :
a- crystals which are dextrorolotary
b- crystals which are levorototary
any compound has plane of symmetry is optical inactive
he has able to separate them (by using a pair of tweezers and magniting
lens ) between right handed crystals and left handed crystals
2- Enzymetic separation :-
this separation can be done in living system , The living system react with
one of the enantiomers and leaving the other .
Pasture found that a yeast in urine reacted with (+) tartaric acid when he
gave the yeast racemic tartaric acid he found that only the dextrorotatory
isomer was consumed , The levorotatory isomers was isolated at the end
of the reaction
3- Separating diastereomers
diastereomers have different physical properties , This fact provides us a
method of resolving a racemic mixture , by reacting of a racemic mixture
with an optically active reagent
Specification of configuration: R and S
Now, a further problem arises. How can we specify a particular
configuration
in some simpler, more convenient way than by always having to draw its
?picture
The most generally useful way yet suggested is the use of the prefixes R and
.S
According to a procedure proposed by R. S. Cahn (The Chemical Society,
,London)
Step 1. Following a set of sequence rules, we assign a sequence of
.priority to the four atoms or groups of atoms attached to the chiral center
In the case of CHClBrI, for example, the four atoms attached to the chiral
center are all different and priority depends simply on atomic number, the
atom
.of higher number having higher priority. Thus I, Br, CI, H
 Br Br
I C Cl Cl C I
H H

Step 2. We visualize the molecule oriented so that the group of lowest

priority
is directed away from us, and observe the arrangement of the remaining
.groups
If, in proceeding from the group of highest priority to the group of second
priority
and thence to the third, our eye travels in a clockwise direction, the
configuration is
specified R (Latin : rectus, right); if counterclockwise, the configuration is
specified
.S (Latin: sinister, left)
:Thus, configurations I and II are viewed like this
 Br Br

H H

I Cl Cl I
  R S
.and are specified R and S, respectively
A complete name for an optically active compound reveals if they are known
both configuration and direction of rotation, as, for example, (S)-(+)-sec-butyl
chloride. A raccmic modification can be specified by the prefix RS, as, for
,example
.sec-butyl chloride-)RS(
We must not, of course, confuse the direction of optical rotation of a
compound a
physical property of a real substance, like melting point or boiling point with
the
direction in which our eve happens to travel when we imagine a molecule held
in an arbitrary manner. So far as we are concerned, unless we happen to know
what has been established experimentally for a specific compound, we have no
idea whether (+ ) or ( - )rotation is associated \\ith the (R)- or the (S)-
.configuration
 H CH3 CH3
1st inversion 2nd inversion
HO C Br HO C Br Br C OH

CH3 H H
S
H CHO CHO
1st inversion 2nd inversion
H3C C Br H3C C Br Br C CH3

CHO H H
R