1

2
Edisson Tello Camacho
 Isomers – Different compounds that
have the same molecular formula.
 Constitutional Isomers – differ
because their atoms are connected in
a different order.

CH3CH2-O-CH2CH3 vs. CH3CH2CH2CH2OH

 Conformational Isomers – differ because of
rotation about single bonds (can
interconvert).

CH3 Br

Br CH3
 Configurational Isomers
– differ in the
arrangement of their atoms in space (cannot
interconvert).

H H H CH3
C C C C
H3C CH3 H3C H
cis-2-butene trans-2-butene
 Configurational Isomers
– differ in the
arrangement of their atoms in space (cannot
interconvert).

H H H Cl

Cl Cl Cl H
cis-1,3-dichlorocyclopentane trans-1,3-dichlorocyclopentane
 Isomerism – The phenomenon whereby
certain chemical compounds have
structures that are different although the
compounds possess the same elemental
composition.

 Isomers – Two or more chemical

substances having the same elementary
composition and molecular weight but
differing in structure.
 Isomerism
 Example C4H10
H
H H H H H H
H C H
H C C C C H
H C C C H
H H H H
H H H
n-Butane Isobutane

These structures are constitutional isomers

These structures are stereoisomers
 Isomerism

Constitutional
Stereoisomers
isomers
Same bond sequences but
Different bond sequences, atoms
different spatial orientation of the
are connected differently.
atoms

Chain
Geometric isomers
Position
Enantiomers and diastereoisomers
Function
 It change in the disposition of the carbon
atoms or carbon skeleton, it means, the
structure could be lineal or branched.
 Is one in which the compounds have the
same carbon skeleton but in which the
functional group or substituent occupies
different position
 Is one in which the functional group varies, but
the carbon skeleton is preserved

The C3H6O may have the isomers:

This isomerism can occur between some related

functional groups such as alcohols and ethers;
acid and esters; aldehydes and ketones
 Exercise:

Draw the next structures:

Two isomers with C2H7N

Five isomers with C6H14
Two isomeric esters with C5H10O2

H3C H3C NH
NH2 CH3
CH3
H3C H3C H3C
H3C H3C
O CH3 CH3 H3C CH3
O O CH3
O CH3 CH3
H3C CH3 H3C
H3C CH3
CH3 H3C
 Constitutional isomers
Different bond sequences, it means
atoms are connected differently.

Chain Position Function

Same function Different
lineal or
but different functional
branched
position gropus
H3C CH3 H3C

CH3 H3C CH3

H3C O O
H3C
CH3
CH3
O H3C

HO CH3 O OH
Exercise
Stablish one chain isomer, one position isomer and one position
isomer for each molecular formula:
 Chain
STRUCTURAL Position
Function

ISOMERS

CONFORMATIONAL (Stereoisomers produced by rotation of

simple bonds)

SPATIAL GEOMETRIC
(Diastereomers cis/trans –
CONFIGURATIONAL E/Z)

OPTICAL
(Enantiomers/
Diastereomers/meso)
CONFORMATION: The different arrangements of atoms that result
from bond rotation are called conformations.
CYCLOHEXANE
 Stereoisomers
Same bond sequences but different
spatial orientation of the atoms

Geometric Function
Cis, trans, E, Z Optical
Isomers Isomers
 GEOMETRIC ISOMERS
1. Are configurational isomers that differ in the spatial position of
substituents around double bond. It is needed two different functional
groups at each end of the double bond

Cis: with the two biggest substituents in the same side

Trans: with the two biggest substituents in opposites positions
 GEOMETRIC ISOMERS
2. Cycloalkanes are less flexible than open-chain alkanes. Because of
their cyclic structures, cycloalkanes have two faces, then its possible
say that if two substituents are oriented to the same face, they will
have cis position, and if they are oriented to opposite faces, they will
have a trans position.

Cis: with the two biggest substituents in the same side

Trans: with the two biggest substituents in opposites positions
 OPTICAL ISOMERS
When compounds have at least one atom with four different
substituents, can be formed two different varieties called optical
isomers, enantiomers or chiral forms.
 Asymmetric carbon or chiral: is the one who will
unite four different groups

 Chiral Compounds: are compounds having at

least one asymmetric center and whose structure
is not superimposable
 Another kind of configurational isomerism.
 Chiral – Nonsuperimposable on its mirror
image.
 Achiral – Superimposable on its mirror
image.
 If a molecule (or object) has a mirror plane
or an inversion center, it cannot be chiral.
 Hammer
 Hammer

achiral
 Brandy snifter
 Brandy snifter

achiral achiral
 Shears
 Shears

chiral
 Beer mug
 Beer mug

achiral
 Hiking boot
 Hiking boot

chiral
 Baseball glove
 Baseball glove

chiral
 Boat propeller
 Boat propeller

chiral
 Desk chair
 Desk chair

achiral
 School desk
 School desk

chiral
 cis-1,3-dimethylcyclopentane
 cis-1,3-dimethylcyclopentane

mirror plane
 cis-1,3-dimethylcyclopentane

achiral

mirror plane
 trans-1,3-dimethylcyclopentane
 trans-1,3-dimethylcyclopentane

chiral
 1,1-dimethylcyclohexane
 1,1-dimethylcyclohexane

achiral
 2-butanol

Copyright © 2010 Pearson

Education, Inc.
 2-butanol

mirror image
Copyright © 2010 Pearson
Education, Inc.
 2-butanol

chiral mirror image

Copyright © 2010 Pearson
Education, Inc.
 2-butanol
Asymmetric
center

chiral mirror image

Copyright © 2010 Pearson
Education, Inc.
 2-butanone
 2-butanone

achiral
 2-bromopropane
 2-bromopropane

achiral
Compounds which specular image is superimposable are identical
(homomerics) and no enantiomers

CH3 H3C

CH3 H3C
H3C CH3

H3C
= CH3

Br Br
 A chiral compound and its mirror image
are called enantiomers.
 2-butanol:
 A chiral compound and its mirror image
are called enantiomers.
 2-butanol:

enantiomers
Copyright © 2010 Pearson
Education, Inc.
 Asparagine:

O OH HO O
C C

H2N C H H C NH2

CH2 CH2
C C
H2N O O NH2
 Asparagine: mirror
plane

O OH HO O
C C

H2N C H H C NH2

CH2 CH2
C C
H2N O O NH2
L-asparagine (from
asparagus) bitter
taste
 Asparagine: mirror
plane

O OH HO O
C C

H2N C H H C NH2

CH2 CH2
C C
H2N O O NH2
L-asparagine (from D-asparagine
asparagus) bitter (from vetch) sweet
taste taste
 Asparagine: mirror
plane

O OH HO O
C C

H2N C H H C NH2

CH2 CH2
C C
H2N O O NH2
L-asparagine (from D-asparagine
asparagus) bitter (from vetch) sweet
taste taste

enantiomers
 Camphor:

O O

enantiomers

Copyright © 2010 Pearson

Education, Inc.
ASIGNACIÓN DE LA CONFIGURACIÓN ABSOLUTA
1 2

3
Nature Chemical Biology 3, 408 - 414 (2007)
 R and S
◦ Look down the bond from the chiral carbon to
the smallest group:

CH 2CH3 1 2
OH HO CH2CH3
H C = C
CH3 CH3
3
 R and S
◦ Look down the bond from the chiral carbon to
the smallest group:

CH 2CH3 1 2
OH HO CH2CH3
H C = C
CH3 CH3
3
 R and S
◦ Assign priorities to the remaining groups based
on atomic numbers.
◦ Clockwise (highest to lowest priority)  R
◦ Counterclockwise  S

CH 2CH3 1 2
OH HO CH2CH3
H C = C
CH3 CH3
3
 R and S
◦ Assign priorities to the remaining groups based
on atomic numbers.
◦ Clockwise (highest to lowest priority)  R
◦ Counterclockwise  S

CH 2CH3 1 2
OH HO CH2CH3
H C = C
CH3 CH3
3
(R)-2-butanol
 Assign priority:
◦ Atomic number of atom directly bonded.
◦ If the same atom is bonded, go to the next
atom, etc.
◦ Groups containing multiple bonds are treated as
though multiple atoms were attached:

N C
C O = C O C N = C N
O C N C
 Determine the absolute configuration of
the following compounds:

3 1
H3C 4 F 4
H H
C C
Cl CH
Br S 2 D R 2 3
1 3

2 O
(CH3)2CHCH2 4
1
H
H C 4
C H

S Cl C
CH3CH2CH2CH2 1 C N
3 CH3CH2 R 2
3
 Determine the absolute configuration of
the following compounds:

3 1
H3C 4 F 4
H H
C C
Cl CH
Br S 2 D R 2 3
1 3

2 O
(CH3)2CHCH2 4
1
H
H C 4
C H

S Cl C
CH3CH2CH2CH2 1 C N
3 CH3CH2 R 2
3
 Determine the absolute configuration of
the following compounds:

3 1
H3C 4 F 4
H H
C C
Cl CH
Br S 2 D R 2 3
1 3

2 O
(CH3)2CHCH2 4
1
H
H C 4
C H

S Cl C
CH3CH2CH2CH2 1 C N
3 CH3CH2 R 2
3
 Determine the absolute configuration of
the following compounds:

3 1
H3C 4 F 4
H H
C C
Cl CH
Br S 2 D R 2 3
1 3

2 O
(CH3)2CHCH2 4
1
H
H C 4
C H

S Cl C
CH3CH2CH2CH2 1 C N
3 CH3CH2 R 2
3
 Determine the absolute configuration of
the following compounds:

3 1
H3C 4 F 4
H H
C C
Cl CH
Br S 2 D R 2 3
1 3

2 O
(CH3)2CHCH2 4
1
H
H C 4
C H

S Cl C
CH3CH2CH2CH2 1 C N
3 CH3CH2 R 2
3
 Determine the absolute configuration of
the following compounds:

3 1
H3C 4 F 4
H H
C C
Cl CH
Br S 2 D R 2 3
1 3

2 O
(CH3)2CHCH2 4
1
H
H C 4
C H

S Cl C
CH3CH2CH2CH2 1 C N
3 CH3CH2 R 2
3
 Determine the absolute configuration of
the following compounds:

3 1
H3C 4 F 4
H H
C C
Cl CH
Br S 2 D R 2 3
1 3

2 O
(CH3)2CHCH2 4
1
H
H C 4
C H

S Cl C
CH3CH2CH2CH2 1 C N
3 CH3CH2 R 2
3
 Determine the absolute configuration of
the following compounds:

3 1
H3C 4 F 4
H H
C C
Cl CH
Br S 2 D R 2 3
1 3

2 O
(CH3)2CHCH2 4
1
H
H C 4
C H

S Cl C
CH3CH2CH2CH2 1 C N
3 CH3CH2 R 2
3
 Determine the absolute configuration of
the following compounds:

3 1
H3C 4 F 4
H H
C C
Cl CH
Br S 2 D R 2 3
1 3

2 O
(CH3)2CHCH2 4
1
H
H C 4
C H

S Cl C
CH3CH2CH2CH2 1 C N
3 CH3CH2 R 2
3
 Determine the absolute configuration of
the following compounds:

CH3 CH3
1 2
CH3O CH 4 CH3O CH 4
H H
C C
2
S CH3 1
R CH3
CH3CH2 CH 3 CH3CH2 CH 3

OH OCH3
1 2
CH2=CH 4 CH2=CH 4
H H
C C
2
S CH3 S C CH
CH3CH2 3 (CH3)2CH 1
3
 Determine the absolute configuration of
the following compounds:

CH3 CH3
1 2
CH3O CH 4 CH3O CH 4
H H
C C
2
S CH3 1
R CH3
CH3CH2 CH 3 CH3CH2 CH 3

OH OCH3
1 2
CH2=CH 4 CH2=CH 4
H H
C C
2
S CH3 S C CH
CH3CH2 3 (CH3)2CH 1
3
 Determine the absolute configuration of
the following compounds:

CH3 CH3
1 2
CH3O CH 4 CH3O CH 4
H H
C C
2
S CH3 1
R CH3
CH3CH2 CH 3 CH3CH2 CH 3

OH OCH3
1 2
CH2=CH 4 CH2=CH 4
H H
C C
2
S CH3 S C CH
CH3CH2 3 (CH3)2CH 1
3
 Determine the absolute configuration of
the following compounds:

CH3 CH3
1 2
CH3O CH 4 CH3O CH 4
H H
C C
2
S CH3 1
R CH3
CH3CH2 CH 3 CH3CH2 CH 3

OH OCH3
1 2
CH2=CH 4 CH2=CH 4
H H
C C
2
S CH3 S C CH
CH3CH2 3 (CH3)2CH 1
3
 Determine the absolute configuration of
the following compounds:

CH3 CH3
1 2
CH3O CH 4 CH3O CH 4
H H
C C
2
S CH3 1
R CH3
CH3CH2 CH 3 CH3CH2 CH 3

OH OCH3
1 2
CH2=CH 4 CH2=CH 4
H H
C C
2
S CH3 S C CH
CH3CH2 3 (CH3)2CH 1
3
 Determine the absolute configuration of
the following compounds:

CH3 CH3
1 2
CH3O CH 4 CH3O CH 4
H H
C C
2
S CH3 1
R CH3
CH3CH2 CH 3 CH3CH2 CH 3

OH OCH3
1 2
CH2=CH 4 CH2=CH 4
H H
C C
2
S CH3 S C CH
CH3CH2 3 (CH3)2CH 1
3
 Determine the absolute configuration of
the following compounds:

CH3 CH3
1 2
CH3O CH 4 CH3O CH 4
H H
C C
2
S CH3 1
R CH3
CH3CH2 CH 3 CH3CH2 CH 3

OH OCH3
1 2
CH2=CH 4 CH2=CH 4
H H
C C
2
S CH3 S C CH
CH3CH2 3 (CH3)2CH 1
3
 Determine the absolute configuration of
the following compounds:

CH3 CH3
1 2
CH3O CH 4 CH3O CH 4
H H
C C
2
S CH3 1
R CH3
CH3CH2 CH 3 CH3CH2 CH 3

OH OCH3
1 2
CH2=CH 4 CH2=CH 4
H H
C C
2
S CH3 S C CH
CH3CH2 3 (CH3)2CH 1
3
 Determine the absolute configuration of
the following compounds:

CH3 CH3
1 2
CH3O CH 4 CH3O CH 4
H H
C C
2
S CH3 1
R CH3
CH3CH2 CH 3 CH3CH2 CH 3

OH OCH3
1 2
CH2=CH 4 CH2=CH 4
H H
C C
2
S CH3 S C CH
CH3CH2 3 (CH3)2CH 1
3
 Properties of the stereoisomers
H OH HO H
H O
-D-glucosa O H -L-glucosa
HO OH
punto fusión 146 HO OH punto fusión 146
enantiómeros HO OH
D H OH HO H D
H H H H

di

os
as

er
ter

m
oi

só
só

i
ro
m

te
er

as
os

di
H OH
H O -D-glucosa
HO punto fusión 148-155
HO H
H D
OH
H OH

Enantiomers Diasteroisomers
Physics properties (density, Peb, Pf etc) y
thermodynamics (DG, DH, DS etc) are Physics properties (densidad, Peb, Pf etc)
identical. and y thermodynamics (DG, DH, DS etc) are
Interaction with the polarized light is different.
opposite.
Spectra NMR, UV/VIS, IR etc son idénticos. Spectra NMR, UV/VIS, IR etc, are different.
DRO, CD are opposite.
 Enantiomers cannot be distinguished
based on physical properties such as
boiling points, melting points, or
densities.
 However—when plane-polarized light is
passed through a solution of one of the
enantiomers, the plane of polarization is
rotated:
 The enantiomer that rotates the plane of
polarized light in a clockwise direction is
called dextrorotatory and is called the
(+)-enantiomer.
 The other enantiomer (counterclockwise
rotation) is levorotatory, the ()-
enantiomer.
 Racemic Mixture: A 50:50 mixture of
two enantiomers – no optical rotation!
 The enantiomer that rotates the plane of
polarized light in a clockwise direction is
called dextrorotatory and is called the
(+)-enantiomer.
 The other enantiomer (counterclockwise
rotation) is levorotatory, the ()-
enantiomer.
 Racemic Mixture: A 50:50 mixture of
two enantiomers – no optical rotation!
 The enantiomer that rotates the plane of
polarized light in a clockwise direction is
called dextrorotatory and is called the
(+)-enantiomer.
 The other enantiomer (counterclockwise
rotation) is levorotatory, the ()-
enantiomer.
 Racemic Mixture: A 50:50 mixture of two
enantiomers – no optical rotation!
  2-chloro-3-iodobutane
H
CH3 Cl Cl H CH3
C C enantiomers C C
I I
H CH3 CH3 H
(2S,3R)-2-chloro-3-iodobutane (2R,3S)-2-chloro-3-iodobutane
erythro erythro

diastereomers diastereomers diastereomers

Cl Cl
CH3 H H CH3
C C enantiomers C C
I I
H CH3 CH3 H
(2R,3R)-2-chloro-3-iodobutane (2S,3S)-2-chloro-3-iodobutane
threo threo
  2-chloro-3-iodobutane
H
CH3 Cl Cl H CH3
C C enantiomers C C
I I
H CH3 CH3 H
(2S,3R)-2-chloro-3-iodobutane (2R,3S)-2-chloro-3-iodobutane
erythro erythro
These two compounds are mirror images.
diastereomers diastereomers diastereomers

Cl Cl
CH3 H H CH3
C C enantiomers C C
I I
H CH3 CH3 H
(2R,3R)-2-chloro-3-iodobutane (2S,3S)-2-chloro-3-iodobutane
threo threo
  2-chloro-3-iodobutane
H
CH3 Cl Cl H CH3
C C enantiomers C C
I I
H CH3 CH3 H
(2S,3R)-2-chloro-3-iodobutane (2R,3S)-2-chloro-3-iodobutane
erythro erythro

diastereomers diastereomers diastereomers

Cl Cl
CH3 H H CH3
C C enantiomers C C
I I
H CH3 CH3 H
(2R,3R)-2-chloro-3-iodobutane (2S,3S)-2-chloro-3-iodobutane
threo threo
  2-chloro-3-iodobutane
H
CH3 Cl Cl H CH3
C C enantiomers C C
I I
H CH3 CH3 H
(2S,3R)-2-chloro-3-iodobutane (2R,3S)-2-chloro-3-iodobutane
erythro erythro

diastereomers diastereomers diastereomers

Note that the absolute configuration for both
Cl asymmetric centers is different. Cl
CH3 H H CH3
C C enantiomers C C
I I
H CH3 CH3 H
(2R,3R)-2-chloro-3-iodobutane (2S,3S)-2-chloro-3-iodobutane
threo threo
  2-chloro-3-iodobutane
H
CH3 Cl Cl H CH3
C C enantiomers C C
I I
H CH3 CH3 H
(2S,3R)-2-chloro-3-iodobutane (2R,3S)-2-chloro-3-iodobutane
erythro erythro

diastereomers diastereomers diastereomers

Cl Cl
CH3 H H CH3
C C enantiomers C C
I I
H CH3 CH3 H
(2R,3R)-2-chloro-3-iodobutane (2S,3S)-2-chloro-3-iodobutane
threo threo
  2-chloro-3-iodobutane
H
CH3 Cl Cl H CH3
C C enantiomers C C
I I
H CH3 CH3 H
(2S,3R)-2-chloro-3-iodobutane (2R,3S)-2-chloro-3-iodobutane
erythro erythro

diastereomers diastereomers diastereomers

Cl Cl
CH3 H H CH3
C C enantiomers C C
I I
H CH3 CH3 H
(2R,3R)-2-chloro-3-iodobutane (2S,3S)-2-chloro-3-iodobutane
threo threo
  2-chloro-3-iodobutane
H
CH3 Cl Cl H CH3
C C enantiomers C C
I I
H CH3 CH3 H
(2S,3R)-2-chloro-3-iodobutane (2R,3S)-2-chloro-3-iodobutane
erythro erythro

diastereomers diastereomers diastereomers

Cl Cl
CH3 H H CH3
C C enantiomers C C
I I
H CH3 CH3 H
(2R,3R)-2-chloro-3-iodobutane (2S,3S)-2-chloro-3-iodobutane
threo threo
  2-chloro-3-iodobutane
H
CH3 Cl Cl H CH3
C C enantiomers C C
I I
H CH3 CH3 H
(2S,3R)-2-chloro-3-iodobutane (2R,3S)-2-chloro-3-iodobutane
erythro erythro
The absolute configuration
diastereomers for diastereomers
one of the asymmetric diastereomers
centers is different, the
other is the same.
Cl Cl
CH3 H H CH3
C C enantiomers C C
I I
H CH3 CH3 H
(2R,3R)-2-chloro-3-iodobutane (2S,3S)-2-chloro-3-iodobutane
threo threo
  2-chloro-3-iodobutane
H
CH3 Cl Cl H CH3
C C enantiomers C C
I I
H CH3 CH3 H
(2S,3R)-2-chloro-3-iodobutane (2R,3S)-2-chloro-3-iodobutane
erythro erythro

diastereomers diastereomers diastereomers

Cl Cl
CH3 H H CH3
C C enantiomers C C
I I
H CH3 CH3 H
(2R,3R)-2-chloro-3-iodobutane (2S,3S)-2-chloro-3-iodobutane
threo threo
  2-chloro-3-iodobutane
H
CH3 Cl Cl H CH3
C C enantiomers C C
I I
H CH3 CH3 H
(2S,3R)-2-chloro-3-iodobutane (2R,3S)-2-chloro-3-iodobutane
erythro erythro

diastereomers diastereomers diastereomers

Cl Cl
CH3 H H CH3
C C enantiomers C C
I I
H CH3 CH3 H
(2R,3R)-2-chloro-3-iodobutane (2S,3S)-2-chloro-3-iodobutane
threo threo
  2,3-dichlorobutane
Cl Cl
CH3 H H CH3
C C enantiomers C C
Cl Cl
H CH3 CH3 H
(2R,3R)-2,3-dichlorobutane (2S,3S)-2,3-dichlorobutane
threo threo
diastereomers
diastereomers

CH3 H CH3 CH3

Cl
C C = C C
Cl Cl Cl
H CH3
H H
(2R,3S)-2,3-dichlorobutane meso
  2,3-dichlorobutane
Cl Cl
CH3 H H CH3
C C enantiomers C C
Cl Cl
H CH3 CH3 H
(2R,3R)-2,3-dichlorobutane (2S,3S)-2,3-dichlorobutane
threo threo
diastereomers
diastereomers

CH3 H CH3 CH3

Cl
C C = C C
Cl Cl Cl
H CH3
H H
(2R,3S)-2,3-dichlorobutane meso
  2,3-dichlorobutane
Cl Cl
CH3 H H CH3
C C enantiomers C C
Cl Cl
H CH3 CH3 H
(2R,3R)-2,3-dichlorobutane (2S,3S)-2,3-dichlorobutane
threo threo
diastereomers
diastereomers
Both asymmetric centers are different.

CH3 H CH3 CH3

Cl
C C = C C
Cl Cl Cl
H CH3
H H
(2R,3S)-2,3-dichlorobutane meso
  2,3-dichlorobutane
Cl Cl
CH3 H H CH3
C C enantiomers C C
Cl Cl
H CH3 CH3 H
(2R,3R)-2,3-dichlorobutane (2S,3S)-2,3-dichlorobutane
threo threo
diastereomers
diastereomers

CH3 H CH3 CH3

Cl
C C = C C
Cl Cl Cl
H CH3
H H
(2R,3S)-2,3-dichlorobutane meso
  2,3-dichlorobutane
Cl Cl
CH3 H H CH3
C C enantiomers C C
Cl Cl
H CH3 CH3 H
(2R,3R)-2,3-dichlorobutane (2S,3S)-2,3-dichlorobutane
threo threo
diastereomers
diastereomers One of the asymmetric centers is different.

CH3 H CH3 CH3

Cl
C C = C C
Cl Cl Cl
H CH3
H H
(2R,3S)-2,3-dichlorobutane meso
  2,3-dichlorobutane
Cl Cl
CH3 H H CH3
C C enantiomers C C
Cl Cl
H CH3 CH3 H
(2R,3R)-2,3-dichlorobutane (2S,3S)-2,3-dichlorobutane
threo threo
diastereomers
diastereomers

CH3 H CH3 CH3

Cl
C C = C C
Cl Cl Cl
H CH3
H H
(2R,3S)-2,3-dichlorobutane meso
  2,3-dichlorobutane
Cl Cl
CH3 H H CH3
C C enantiomers C C
Cl Cl
H CH3 CH3 H
(2R,3R)-2,3-dichlorobutane (2S,3S)-2,3-dichlorobutane
threo threo
diastereomers
diastereomers

CH3 H CH3 One of CH

Cl 3
the asymmetric centers is different.
C C = C C
Cl Cl Cl
H CH3
H H
(2R,3S)-2,3-dichlorobutane meso
  2,3-dichlorobutane
Cl Cl
CH3 H H CH3
C C enantiomers C C
Cl Cl
H CH3 CH3 H
(2R,3R)-2,3-dichlorobutane (2S,3S)-2,3-dichlorobutane
threo threo
diastereomers
diastereomers

CH3 H CH3 CH3

Cl
C C = C C
Cl Cl Cl
H CH3
H H
(2R,3S)-2,3-dichlorobutane meso
  2,3-dichlorobutane
Cl Cl
CH3 H H CH3
C C enantiomers C C
Cl Cl
H CH3 CH3 H
(2R,3R)-2,3-dichlorobutane (2S,3S)-2,3-dichlorobutane
threo threo
diastereomers
diastereomers
Mirror plane!
CH3 H CH3 CH3
Cl This diastereomer is
C C = C C achiral!
Cl Cl Cl
H CH3
H H
(2R,3S)-2,3-dichlorobutane meso
  2,3-dichlorobutane
Cl Cl
CH3 H H CH3
C C enantiomers C C
Cl Cl
H CH3 CH3 H
(2R,3R)-2,3-dichlorobutane (2S,3S)-2,3-dichlorobutane
threo threo
diastereomers
diastereomers

CH3 H CH3 CH3

Cl
C C = C C
Cl Cl Cl
H CH3
H H
(2R,3S)-2,3-dichlorobutane meso
 Erythrose
O CHO CHO
OH
H C H H C OH H C OH
C C = =
H C OH H C OH
H CH2OH
HO CH2OH CH2OH
 Erythrose
O CHO CHO
OH
H C H H C OH H C OH
C C = =
H C OH H C OH
H CH2OH
HO CH2OH CH2OH
Fischer projection
of D-erythrose
 Erythrose
O CHO CHO
OH
H C H H C OH H C OH
C C = =
H C OH H C OH
H CH2OH
HO CH2OH CH2OH
Fischer projection
of D-erythrose
◦ If the substituents are eclipsed in the Fischer
projection, it is the erythro diastereomer.
 Threose
O CHO CHO
OH
H C H HO C H HO C H
C C = =
H C OH H C OH
HO CH2OH
H CH2OH CH2OH
Fischer projection
of D-threose
◦ If the substituents are not eclipsed in the
Fischer projection, it is the threo
diastereomer.
 ()-Ephedrine
CH3 C6H5
HN H HO C H
C =
C CH3 CH3NH C H
H OH CH3
 ()-Ephedrine
CH3 C6H5
HN H HO C H
C =
C CH3 CH3NH C H
H OH CH3

A component of “Ma Huang”

(Ephedra sinica)
 ()-Ephedrine
CH3 C6H5
HN H HO C H
C =
C CH3 CH3NH C H
H OH CH3
Erythro diastereomer

A component of “Ma Huang”

(Ephedra sinica)
 ()-Ephedrine
CH3 C6H5
HN H HO C R H
C =
C CH3 CH3NH C H
S
H OH CH3
Erythro diastereomer

A component of “Ma Huang”

(Ephedra sinica)
 (+)-Pseudoephedrine
CH3 C6H5
HN H H C OH
C =
C CH3 CH3NH C H
HO H CH3
 (+)-Pseudoephedrine
CH3 C6H5
HN H H C OH
C =
C CH3 CH3NH C H
HO H CH3

The active ingredient in the

decongestant Sudafed®
 (+)-Pseudoephedrine
CH3 C6H5
HN H H C OH
C =
C CH3 CH3NH C H
HO H CH3
Threo diastereomer

The active ingredient in the

decongestant Sudafed®
 (+)-Pseudoephedrine
CH3 C6H5
HN H H C OH
= S
C
C CH3 CH3NH C H
S
HO H CH3
Threo diastereomer

The active ingredient in the

decongestant Sudafed®
 CH3 CH CH CO2H
HO NH2
 Indicate the asymmetric carbons in threonine.
 Draw all of the stereoisomers of threonine.

 Identify which are enantiomers and which are

diastereomers.
 CH3 CH CH CO2H an amino acid (one of the
building blocks of proteins)
HO NH2
 Indicate the asymmetric carbons in threonine.
 Draw all of the stereoisomers of threonine.

 Identify which are enantiomers and which are

diastereomers.
 CH3 CH CH CO2H an amino acid (one of the
building blocks of proteins)
HO NH2
 Indicate the asymmetric carbons in threonine.
 Draw all of the stereoisomers of threonine.

 Identify which are enantiomers and which are

diastereomers.
 CH3 CH CH CO2H an amino acid (one of the
building blocks of proteins)
HO NH2
 Indicate the asymmetric carbons in threonine.
 Draw all of the stereoisomers of threonine.

 Identify which are enantiomers and which are

diastereomers.
 CH3 CH CH CO2H an amino acid (one of the
building blocks of proteins)
HO NH2
 Indicate the asymmetric carbons in threonine.
 Draw all of the stereoisomers of threonine.

 Identify which are enantiomers and which are

diastereomers.
 CH3 CH CH CO2H an amino acid (one of the
building blocks of proteins)
HO NH2
 Indicate the asymmetric carbons in threonine.
 Draw all of the stereoisomers of threonine.
CO2H CO2H CO2H CO2H
H C NH2 H2N C H H C NH2 H2N C H

HO C H H C OH H C OH HO C H
CH3 CH3 CH3 CH3

 Identify which are enantiomers and which are

diastereomers.
 CH3 CH CH CO2H an amino acid (one of the
building blocks of proteins)
HO NH2
 Indicate the asymmetric carbons in threonine.
 Draw all of the stereoisomers of threonine.
CO2H CO2H CO2H CO2H
H C NH2 H2N C H H C NH2 H2N C H

HO C H H C OH H C OH HO C H
CH3 CH3 CH3 CH3
 Identify which are enantiomers and which are
diastereomers.
 an amino acid (one of the
CH3 CH CH CO2H building blocks of proteins)
HO NH2
 Indicate the asymmetric carbons in threonine.
 Draw all of the stereoisomers of threonine.
CO2H CO2H CO2H CO2H
H C NH2 H2N C H H C NH2 H2N C H

HO C H H C OH H C OH HO C H
CH3 CH3 CH3 CH3
D-threonine L-threonine D-allothreonine L-allothreonine
The only one that works
for building proteins
 Identify which are enantiomers and which are
diastereomers
 HOCH2 O OH a sugar unit in ribonucleic
acid (RNA)
H H
H Note: deoxyribose (from
DNA) is missing the 2-OH
HO OH

 Indicate the asymmetric carbons in ribose.

 HOCH2 O OH a sugar unit in ribonucleic
acid (RNA)
H H
H Note: deoxyribose (from
DNA) is missing the 2-OH
HO OH

 Indicate the asymmetric carbons in ribose.

 HOCH2 O OH a sugar unit in ribonucleic
acid (RNA)
H H
H Note: deoxyribose (from
DNA) is missing the 2-OH
HO OH

 Indicate the asymmetric carbons in ribose.

 HOCH2 O OH a sugar unit in ribonucleic
acid (RNA)
H H
H Note: deoxyribose (from
DNA) is missing the 2-OH
HO OH

 Indicate the asymmetric carbons in ribose.

HOCH2 O OH a sugar unit in ribonucleic
acid (RNA)
H H
H Note: deoxyribose (from
DNA) is missing the 2-OH
HO OH

 Indicate the asymmetric carbons in ribose.

HOCH2 O OH a sugar unit in ribonucleic
acid (RNA)
H H
H Note: deoxyribose (from
DNA) is missing the 2-OH
HO OH

 Indicate the asymmetric carbons in ribose.

 Assign absolute configurations to each of the
asymmetric carbon atoms.
HOCH2 O R
OH a sugar unit in ribonucleic
R acid (RNA)
H H
R R Note: deoxyribose (from
H
DNA) is missing the 2-OH
HO OH

 Indicate the asymmetric carbons in ribose.

 Assign absolute configurations to each of the
asymmetric carbon atoms.
HOCH2 O R
OH a sugar unit in ribonucleic
R acid (RNA)
H H
R R Note: deoxyribose (from
H
DNA) is missing the 2-OH
HO OH

 Indicate the asymmetric carbons in ribose.

 Assign absolute configurations to each of the
asymmetric carbon atoms.
 How many stereoisomers are theoretically
possible for ribose?
HOCH2 O R
OH a sugar unit in ribonucleic
R acid (RNA)
H H
R R Note: deoxyribose (from
H
DNA) is missing the 2-OH
HO OH
 Indicate the asymmetric carbons in ribose.
 Assign absolute configurations to each of the
asymmetric carbon atoms.
 How many stereoisomers are theoretically
possible for ribose? 4 asymmetric centers: 24 =
16.
 OH
O
H2N
O O
OH
OH OH
HO OH
OH
HO
OH
CH3
HO OH
OH OH
OH

from the Hawaiian coral “Limu-make-o-

OH

Hana”, Palythoa toxica. O
OH

 The most poisonous non-protein substance OH

known. HO
 LD50 (mice) = 50 ng/kg i.p. OH OH
O
64 asymmetric centers!
HO OH
 O CH3 OH CH3 OH HO
OH OH
N O
H H OH
OH OH HO
HO N O H3C O OH HO
H
OH
O CH3 OH OH
H 3C O
CH3
OH OH
HO OH
OH
 OH
O
H2N
O O
OH
OH OH
HO OH
OH
HO
OH
CH3
HO OH
OH OH
OH

from the Hawaiian coral “Limu-make-o-

OH

Hana”, Palythoa toxica. O
OH

 The most poisonous non-protein substance OH

known. HO
 LD50 (mice) = 50 ng/kg i.p. OH OH
O
64 asymmetric centers!
HO OH
 O CH3 OH CH3 OH HO
OH OH
N O
H H OH
OH OH HO
HO N O H3C O OH HO
H
OH
O CH3 OH OH
H 3C O
CH3
OH OH
HO OH
OH
 OH
O
H2N
O O
OH
OH OH
HO OH
OH
HO
OH
CH3
HO OH
OH OH
OH

from the Hawaiian coral “Limu-make-o-

OH

Hana”, Palythoa toxica. O
OH

 The most poisonous nonprotein substance OH

known. HO
◦ LD50 (mice) = 50 ng/kg i.p. OH OH
O
64 asymmetric centers!
HO OH
 O CH3 OH CH3 OH HO
OH OH
N O
H H OH
OH OH HO
HO N O H3C O OH HO
H
OH
O CH3 OH OH
H 3C O
CH3
OH OH
HO OH
OH
 OH
O
H2N
O O
OH
OH OH
HO OH
OH
HO
OH
CH3
HO OH
OH OH
OH
OH
 from the Hawaiian coral “Limu-make-o-
Hana”, Palythoa toxica. O
OH

 The most poisonous nonprotein substance OH

known. HO
◦ LD50 (mice) = 50 ng/kg i.p. OH OH
O
64 asymmetric centers!
HO OH
 O CH3 OH CH3 OH HO
OH OH
N O
H H OH
OH OH HO
HO N O H3C O OH HO
H
OH
O CH3 OH OH
H 3C O
CH3
OH OH
HO OH
OH
 Free radical bromination of butane:

H
C Br2
CH3 H C CH3
H h
CH2CH3 CH2CH3

Br CH2CH3
H CH3
C + C
H CH3
CH2CH3 Br
(S)-2-Bromobutane (R)-2-Bromobutane
 Free radical bromination of butane:

H
C Br2
CH3 H C CH3
H h
CH2CH3 CH2CH3

Br CH2CH3
H CH3
C + C
H CH3
CH2CH3 Br
(S)-2-Bromobutane (R)-2-Bromobutane
 Free radical bromination of butane:

H
C Br2
CH3 H C CH3
H h
CH2CH3 CH2CH3
a trigonal-planar intermediate
Br CH2CH3
H CH3
C + C
H CH3
CH2CH3 Br
(S)-2-Bromobutane (R)-2-Bromobutane
 Free radical bromination of butane:

H
C Br2
CH3 H C CH3
H h
CH2CH3 CH2CH3
a trigonal-planar intermediate
Br CH2CH3
H CH3
C + C
H CH3
CH2CH3 Br
(S)-2-Bromobutane (R)-2-Bromobutane
 Free radical bromination of butane:

H
C Br2
CH3 H C CH3
H h
CH2CH3 CH2CH3
a trigonal-planar intermediate
Br CH2CH3
H CH3
C + C
H CH3
CH2CH3 Br
(S)-2-Bromobutane (R)-2-Bromobutane

a racemic mixture
 Free radical chlorination of (S)-2-
bromobutane
◦ Attack at C(2):
Br
Cl2
C Br C CH3
H CH3 h CH2CH3
CH2CH3
(S)-2-Bromobutane

Br CH2CH3
Cl CH3
C + C
Cl CH3
CH2CH3 Br
 Free radical chlorination of (S)-2-
bromobutane
◦ Attack at C(2):
Br
Cl2
C Br C CH3
H CH3 h CH2CH3
CH2CH3
(S)-2-Bromobutane trigonal-planar intermediate
Br CH2CH3
Cl CH3
C + C
Cl CH3
CH2CH3 Br
 Free radical chlorination of (S)-2-
bromobutane
◦ Attack at C(2):
Br
Cl2 CH3
C Br C
H CH3 h CH2CH3
CH2CH3
(S)-2-Bromobutane trigonal-planar intermediate
Br CH2CH3
Cl CH3
C + C
Cl CH3
CH2CH3 Br
a racemic mixture
 Free radical chlorination of (S)-2-
bromobutane
◦ Attack at C(3):
Br H Br
Cl2 H
C C C C
CH3 H h CH3 CH3
H CH3 H
2S
Br H Br Cl
CH3
C C + CH C C H
CH3 3
Cl
H H CH3
2S,3R 2S,3S
major minor
 Free radical chlorination of (S)-2-
bromobutane
◦ Attack at C(3):
Br H Br
Cl2 H
C C C C
CH3 H h CH3 CH3
H CH3 H
2S trigonal-planar intermediate
Br H Br Cl
CH3
C C + CH C C H
CH3 3
Cl
H H CH3
2S,3R 2S,3S
major minor
 Free radical chlorination of (S)-2-
bromobutane
◦ Attack at C(3):
Br H Br
Cl2 H
C C C C
CH3 H h CH3 CH3
H CH3 H
2S
Br H Br Cl
CH3
C C + CH C C H
CH3 3
Cl
H H CH3
2S,3R 2S,3S
major minor
a mixture of
diastereomers
 Free radical chlorination of (S)-2-
bromobutane
◦ Attack at C(3):
Br H Br
Cl2 H
C C C C
CH3 H h CH3 CH3
H CH3 H
2S
Br H Br Cl
CH3
C C + CH C C H
CH3 3
Cl
H H CH3
2S,3R 2S,3S
major minor
a mixture of
diastereomers
 Amphetamine
CH3 CH3 Synthetic
C + C amphetamine is a
H H CH2Ph racemic mixture.
PhCH2
NH2 H2 N

CO2H
H C OH
HO C H
CO2H

CO2H CO2H
CH3 CH3
H C OH H C OH
C
H + H C
PhCH2 HO C H CH2Ph HO C H
NH3 H3 N
CO2 CO2
 Amphetamine
CH3 CH3 Synthetic
C + C amphetamine is a
H H CH2Ph racemic mixture.
PhCH2
NH2 H2 N

CO2H
H C OH
Add L-tartaric acid.
HO C H
CO2H

CO2H CO2H
CH3 CH3
H C OH H C OH
C
H + H C
PhCH2 HO C H CH2Ph HO C H
NH3 H3 N
CO2 CO2
 Amphetamine
CH3 CH3 Synthetic
C + C amphetamine is a
H H CH2Ph racemic mixture.
PhCH2
NH2 H2 N

CO2H
H C OH
Add L-tartaric acid.
HO C H
CO2H

CO2H CO2H
CH3 CH3
H C OH H C OH
C
H + H C
PhCH2 HO C H CH2Ph HO C H
NH3 H3 N
CO2 CO2
Get a mixture of diastereomeric salts (crystalline).
 Amphetamine

Separate the diastereomers

by recrystallization.
CO2H
CH3 CH3
H C OH 10% H2SO4
H
C 2 H C SO42-
CH2Ph HO C H CH2Ph
H3 N H3 N
CO2
 Amphetamine

Separate the diastereomers

by recrystallization.
CO2H
CH3 CH3
H C OH 10% H2SO4
H
C 2 H C SO42-
CH2Ph HO C H CH2Ph
H3 N H3 N
CO2
Isolate the pure (+)
enantiomer as the sulfate salt.

Copyright © 2010 Pearson

Education, Inc.