Chapter 4

organic chemistry based on the relationship between molecular structure and

properties

three dimensional structure ; stereochemistry

stereoisomer ; diIIerent orientation oI atoms in space

conIormational analysis, enantiomer, diastereomer

the structure oI CH

beIore the direct determination

CH

Y ; only one compd

square planar
pyramidal
tetrahedral
CH

XY ; only one compd

CWXYZ ; two compds
tetrahedral
tetrahedral
enantiomer
optically active substance rotate the plane oI polarized light
polarimeter
Eig 4-2
optically inactive
optically active
dextrorotatory
levorotatory

optical rotation depends

on the concn
speciIic rotation | | /l d | |

(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

CHOHCOOH the same acid

strength
*



with optically
active reagents,
the results will
be diIIerent
Irom the same
products with
the same rates
alkene
H

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

X-ray diIIraction can determine

the conIiguration oI a particular enantiomer
time-consuming
applied only to certain compds
the chemical conversion
should not involve
the chiral center.
use chemical conversion oI
a compd with the known
conIiguration to the compd
to be examined.
retained
conIiguration
*

C CH

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

racemization is not likely

with optically active RH
expect racemization
with optically active RH



Me
C
ClH

C
Et
H
racemic pdt
( S ) - ( )