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[Cr(H2O)6]3+
CHF2Cl
CF4
Stereochemistry
Isomerism
Structural
Chain
Functional
Stereoisomerism
Conformational
Configurational
Positional
Eclipsed
Staggered
Gauche
Optical
Geomet
rical
COOH
COOH
HO
H3C
OH
CH3
d-lactic acid
l-lactic acid
A carbon atom or center containing four different substituents is called as chiral carbon/
chiral center.
R
R
+
R
2
R
Chiral compound
R
2
R
Chiral compound
R1
R2
R4
R3
R5
Chiral compound
Center of symmetry
Plane of symmetry
CH3
COOH
b
a
d
b
COOH
Elements of
symmetries
Ph
Ha
Hd
Hb
Hd
Hb
Ha
H
CH3
Alternative axis of
symmetry
Axis of symmetry
plane of symmetry
Hb
Ha
Hd
COOH
COOH
H
Ph
Center of symmetry
(a)
H
COOH Ph
Ph
H
Ph
COOH
Plane refle
ction
COOH
COOH
H
Ph
(a)
Enantiomers
O
Disteriomers
R
NH
OH
NH
OH
S - isomer,
beta -blocker
R - isomer,
Contraceptive
Optical Active
compounds
Epimers
CHO
CHO
H
HO
H
* OH
* H
* OH
CH2OH
Epimers
HO
* H
HO
* H
* OH
CH2OH
COOH
H
OH
OH
COOH
plane of symmetry
Enantiomers
NH
R
O
OH
OH
Et
NH
H
OH
NH
NH
Et
H
OH
S - isomer,
beta -blocker
NH
NH
Et
H
OH
(S,S) -isomer
Tuberculostatic
R - isomer,
Contraceptive
OH
Et
(R,R)-isomer
Cause blindness
Ethambutol
The mixtures of equal amounts of enantiomers (d and l form) are optically inactive are
called as racemic mixtures (dl)
Many of the
chemical
reactions are
similar but few of
them are different
They may have
different energy of
activation,
resulting the
different reaction
rates
Disteriomers
The stereoisomers which are not mirror images of each others are called as
disteriomers
H
HO
OH
HO
H
COOH
(I)
Enantiomers
COOH
COOH
COOH
COOH
OH
HO
OH
OH
HO
COOH
(II)
COOH
COOH
(IV)
(III)
mesoform (inactive)
I and III, I and IV, II and III, II and IV are disteriomers of each others
Epimers
CHO
H
* OH
HO
* H
* OH
CH2OH
Epimers
HO
* H
HO
* H
* OH
CH2OH
Some compounds possesses chiral carbon atoms can show optical inactivity
Reasons
1. Due to internal compensation:
In meso form of the molecule, one half of the
molecule is the mirror image of the other
half; thus if one half of the molecule rotates
the light towards the right, the other half
would rotates it to the same extent towards
the left. Therefore no deflection of the light
is observed due to intrinsic property of the
molecule
COOH
H
OH
OH
COOH
plane of symmetry
dl Nomenclature
(obtained by comparing
with glyceraldehyde
Absolute or RS
nomenclature
2
1
R (Rectus means
right handed)
Sequence rule
4
R
Clockwise rotation
2
3
4
S
Anticlockwise rotation
S (Sinister means
left handed)
Priority
rule/Sequence rule
Rules used to decide the priority order of the groups of atoms or atoms attached to chiral center
X
Chiral Molecule
1. The atom having highest atomic number (atomic mass) was given highest priority and
the atom with the lowest atomic number has lowest priority.
1-Chloroethanol. The four atoms/groups attached to chiral carbon are Cl, OH, CH3, and H.
The priority order of substituents according to the atomic number are Cl>O>C>H. Therefore
the priority order of the four atoms/groups is Cl > OH > CH3 > H.
CH3
HO
Cl
CH
C C
1
C C
C C
Triple bond replaced by-
CH CH2
H2
CH C
2
C C
double bond replaced by-
4. In case the molecules have two isotopes of the same element attached to
the chiral carbon atom, higher priority is given to the heavier isotope. For
example deuterium would get priority over hydrogen and C-13 would set
priority over C-12.
The symbol R comes from the Latin rectus for right, and S from the Latin sinister for left.
Lowest Priority
group away from
viewer
CHO
CHO
H
OH
converted to
CH2OH
H
OH
(II)
(Tetrahedral form)
CH2OH
(I)
(Planar structure)
Determination of
R/S configuration
The plane projection diagram of glyceraldehydes
molecule I is converted to the tetrahedral form structure II
places the CH2OH furthest away from the eye. To
determine the R and S configuration of the molecule, the
lowest priority group should occupy the position, furthest
from the eye. Therefore to determine configuration, the
hydrogen atom should be occupy the position occupied
by CH2OH group and hence interchange of the positions
of the groups are required
CHO
HOH 2C
Backside
position
H
OH
CHO
1st interchnage
H
OH
HOCH2
between H
CH2 OH and CH2OH
(I)
CHO
OH
H
OH
2nd interchange
between OH
and CHO
HOCH2
CHO
H
H
HOCH2
CHO
'R'
CH2OH
tetrahedral form
title as suggested
by Fischer
away to viewer
H
OHC
OH
CH2OH towards viewer
CHO
H
vertical line
OH
CH2OH
horizontal line
planar structure
C2 H5
CH3
H
180
CH3
Br
'R'
Rotation
H
C2 H5
C2 H5
C2 H5
1st interchange
H
of H and Et
CH3
Br
C2 H5
C2 H5
2nd interchange
of H and Br
Br
CH3
H
Br
CH3
H
'R'
C2 H5
CH3
H
90
'R'
Rotation
CH3
H
C2 H5
Br
C2 H5
CH3
1st interchange
of H and Et
C2 H5
Br
H
C2 H5
C2 H5
2nd interchange
of Me and Et
H3C
Br
H
CH3
Br
H
'S'
OH
OH
CH2OH
H
H
OH
OH
CHO
CH2OH
Eclipsed conformation
OH
OH
CH2 OH
CHO
CHO
H
R
H
Erythreose
OH
of H and R
OH
CHO
1st interchange
R
OH
CHO
2nd interchange
of R and OH
HO
R = -CHOH-CH2OH
R
H
CHO
H
HO
R
'R'
Working out the configuration of carbon atom C3, the steps adopted are as follows.
CHO
OH
OH
CH2 OH
Erythreose
R
H
CH2 OH
H
OH
OH
1st interchange
CH2 OH
HOCH2
of H and CH2OH
R
H
2nd interchange
HO
OH
of CH2OH and OH
R = -CHOH-CHO
R
CH2OH
H
R
H
HO
CH2 OH
'R'
X
N
X
z
(Pyramidal inversion)
z
Y
The inversion is less in substituted amines and amides. Two types of nitrogen
atom invert slowly as nitrogen in three membered ring and nitrogen connected to
another atom bearing lone pair of electrons. In some molecules in which nitrogen
atom is at a bridgehead, pyramidal inversion is prevented.
mirror
Cl
Cl
N
CH3
Cl
H3C
CH3
N
CH3
Cl
CH3
H3C
(cis)
(trans)
As
H3C
Ph
Et
Me
R
RO
O
S
R'
OR'
OR'
R''
S+ X
R'
R
A
B
A
B
Prochiral relationship:
When chiral center is produced after the substitution reaction in the
original center or assembly is known as prochiral center.
e.g. 1,3-Propane diol. If -H hydrogen atom undergoes deuteration in
presence of suitable catalyst forming two identical compound is optically
inactive. The protons at C2 is symmetric are called as homotopic ligands.
HO
H D
H H
OH
HO
OH
HO
H
OH
replace beta H
replace alpha-H
by D
by D
HO
Optically inactive
C2 substitution
OH
pro-R hydrogen
H D
beta-H substitution
OH
HO
H
HO
OH
C1/C3 substitution
pro-S hydrogen D
H
alpha-H substitution
Prochiral faces
There are two faces for the chiral carbons as Si-face and Re-face. In
Si-face we obtained S configuration in prochiral carbon. In Re-face
we obtained R configuration in prochiral carbon. E.g. Reduction of
deutarated acetaldehyde.
We can distinguish these two products by asymmetric reaction. In
above example, there is formation of only R-1-deutarated ethanol
indicates that attack of H takes from Si face only.
CH3
HO
D
'R'
H2/Si face
attack from
backside
H3C
H2/Re face
D
attack from
frontside
CH3
D
D
HO
'S'