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(dm) (g/cm
)
X
Y
W
Z
X
Y
W
Z mirror image
not superimposible
enantiomer
non superimposable molecules
on their mirror images chiral can exist as enantiomers
achiral
chiral molecule
achiral molecule
chiral center
(chiral carbon)
carbon atom to have Iour
diIIerent groups
have more than one
chiral center
molecules without chiral
centers can be chiral
enantiomers have identical physical properties
except Ior the direction oI rotation oI the
plane oI polarized light
enantiomers have identical
chemical properties except
toward optically active reagents
CH
SO
HBr
CH
COOH
alkyl bromide
ester
CH
CHCH
OH CH
CH
*
( transition states are
not mirror images)
(transition states are mirror images)
a mixture oI eaqual amounts
oI enantiomers
racemic modiIication
optically inactive
( )
inseparable by
usual methods
resolution
the material containing
an excess oI one enantiomer
shows optical activity
iI there is no rapid
interconversion
conIigurational
enantiomers
conIormational
enantiomers
no interconversion
easy interconversion
conIiguration ; the arrangement
oI atoms that
characterizes
a particular
stereoisomer.
how to assign
conIiguration?
X-ray analysis
derivatization
how to speciIy conIiguration
1) assign a sequence oI priority
2) R ; clockwise
S ; counterclockwise
sec-butyl chlorides
Cl
H
C
H
C
Cl
CH
H
C
C CH
CH
C
H
Cl
CH
Cl
*
Br Br
H
H
Cl
I I Cl
( R ) ( S )
CA
C A
C
A
A C
A
C
A
A
C
C
(RS) Ior racemic
C CH
H
NH
CH
CH
*
CH
CH C
CH
CH
H
C CH
CH
C
,
CHO
C
CH
OH
H OH
*
ex)
*
CH
CH
CH CH
Cl
CH
*
Cl
*
CH
CH
CH
Cl H
H Cl
CH
CH
CH
Cl H
Cl H
CH
CH
CH
H Cl
H Cl
CH
CH
CH
Cl
Cl
H
H
(not superimposable)
enantiomers
(not superimposible)
enantiomers
diastereomer (not mirror images)
compounds containing more
than one chiral center
diastereomers ; diIIerent chemical & physical properties
can be separated by usual methods
4 possible stereoisomers
Ior n chiral centers 2
possible isomers
CH
CH CH
Cl
CH
*
Cl
*
CH
CH
Cl H
H Cl
CH
CH
Cl H
Cl H
CH
CH
H Cl
H Cl
CH
CH
Cl
Cl
H
H
enantiomers
(not superimposible)
meso compd
(superimposible)
CH
CH
CH CH
Cl
CH
*
Cl
*
CH
CH CH
Cl
CH
*
Cl
*
( 2S, 3S )
. . . .
( S, S )
. . . .
optically inactive
have a plane oI summetry
examine superimposability
& interconvertibility
conIormational isomer (conIormer)
conIigurational isomer (inversional isomer)
3 2
CH
CH
CH
CH
Cl
h or
C
C
C H
Cl
R & S
(racemic modiIication)
the same chance to
attack each Iace
chiral pdts Irom achiral
reactants are racemic
modiIication
inseparable by
usual methods
optically inactive reactants give
optically inactive products
CH
CH
CHClCH
C Cl
CH
H
C
*
( S )
Cl
C Cl
CH
H
C
Cl
*
C Cl
CH
Cl
H
C
CH
H
C
OH C CH
CH
H
C
Cl
HCl
( S ) - ( ) ( S ) - ( )
ex)
C COOH
CH
H
C
( S ) - ( )
KMnO
speciIic rotation
1.67 dextrorotatory
optically pure
0.835 :
75 ( S ) - ( )
25 ( R ) - ( )
-5.90
have 50 optical purity
pure ( S ) - ( )-2-methyl-1-butanol
( S ) -1-chloro-2-methylbutane
Cl
CH
CH
CH CH
Cl
*
CH
CH CH
Cl
*
CH
Cl
three possible isomers
Cl
H Me
CH
CH
C
Me
Cl
H
Cl
C
C
Me
Cl
H
H
Me
Me H
a b
a
b
Cl
H Me
H Me
c
d
( I ) ( II )
( S )
1) the conIiguration oI the orginal chiral center
is retained.
2) attack Irom a, d
attack Irom b, c
( S, S )
( R, S or meso )
3) attacking chances are diIIerent
conIormation ( I )
conIormation ( II )
4) conIormation ( I ) is Iavored over ( II )
5) ( S, S ) / ( R, S ) 29 / 71
6) Irom ( R )-isomer oI sec-butyl choride ( R, R ) / ( R, S ) 29/71
7) racemic sec-butyl chloride optically inactive pdts
b is Iavored
d is Iavored
CH
CH
CH
CH
Cl
CH
H H
H
C H
CH
H H
H CH
racemic
modiIication
cI)
resolution oI
a racemic
modiIication
( ) - HA
( ) - HA
( ) - B
| ( + ) - A ( ) - BH |
| ( ) - A ( ) - BH | ( ) - HA
( +) - HA
racemic optically
active
diastereomer
separable
What is the stereochemistry oI rxns
in which the bonds to the chiral center
are broken ?
depends on the mechanism
ex) Ior halogenation, two possible mechnisms
X RH HX R
R X
RX X
X RH RX H
H X
HX X
C
Et
H
racemic pdt
( S ) - ( )