R-enantiomer (Clockwise Rotation)

S-enantiomer (Counterclockwise Rotation)

Assigning R and S Configuration to Fischer Projections
1. Assign priorities to the four substitutents according to the Cahn-Ingold-Prelog
rules
2. Perform the two allowed manipulations of the Fischer projection to place the
lowest priority group at the top or bottom).
3. If the priority of the groups 123 are clockwise then assign the center as
R, if 123 are counterclockwise then assign
the center as S.
2 place at
CO2H the top 4
H
1 H2N H 4 2 HO2C NH2 1
hold steady CH3 CH3
rotate other 3 3
three groups
counterclockwise
1-2-3 counterclockwise = S
2
4 2
CO2H
H CO2H
4 H 1 2
NH2 1 H2N
H2N CO2H CH3
CH3 1 3
CH3 H
3 4
3

1-2-3 clockwise = R
 E/Z nomenclature
• IUPAC system for naming alkene isomers, called the E-Z system,
is based on the same priority rules. The general strategy of
the E-Z system is to analyze the two groups at each end of the
double bond.
• Higher priority group at one end of the double bond and the
higher priority group at the other end of the double bond are on
the same side (Z, from German zusammen = together) or
on opposite sides (E, from German entgegen = opposite) of the
double bond.
• Ex:
RS nomenclature of cyclohexane system
Above Adamentane derivative can be regarded as the
formal derivative of 2-bromopropionic acid
 Chiral compounds with no stereogenic centres: Axial Chirality
Axial chirality is a special case of chirality in which a molecule does not possess
a conventional chiral center (stereogenic centre) but an axis of chirality, an axis about
which a set of substituents is held in a spatial arrangement that is not superposable on its
mirror image. Axial chirality is most commonly observed
in atropisomeric substituted biaryl compounds wherein the rotation about the aryl–aryl
bond is restricted. Certain allene compounds and spirans also display axial chirality.
AXIAL CHIRALITY: Nonplanar arrangement of four groups around an axis
 Mycomycin, an antibiotic
H
H
C C C
H C C C C
CH=CHCH=CHCH2CO2H
o
Nocardia acidophilus []D = -130

H H
H H
C C C C C C
Cl Cl
CH3 CH3
 Atropisomers

• Atropisomers are stereoisomers resulting from hindered rotation

about single bonds where the steric strain barrier to rotation is
high enough to allow for the isolation of the conformers (from
Greek, a = not and tropos = turn).

• The name was introduced by Kuhn in 1933, but atropisomerism

was first detected in 6,6ʼdinitro-2,2ʼ-diphenic acid by Cristie in
1922.

• Atropisomers are detectable by NMR if half lives exceed 10-12 sec

• Atropisomers are isolable if the half-life is above 1000 sec.

 Tutorial
 Find the stereocenters (R/S) for the following compounds
R and S Assignments in Compounds with Two or More
Stereogenic Centers.

• When a compound has more than one stereogenic center, the R and S configuration
must be assigned to each of them.

One stereoisomer of 2,3-dibromopentane

The complete name is (2S,3R)-2,3-dibromopentane

 Diastereoisomers
• Diastereoisomers are stereoisomers that are not mirror images.
Two diastereoisomers are different compound, and have different
relative stereochemistry.
• Diastereoisomers may be achiral or chiral.
• Diastereoisomers can arise when structures have more than one
stereogenic center.
Is there a chemical difference between two enantiomers?
Take (S)-alanine (alanine extracted from plants) and (R)-alanine (the
enantiomer found in bacterial cell walls) as examples.

They both have identical NMR spectra, identical IR spectra, and

identical physical properties, identical chemical properties in achiral
environment with two important exceptions.
If you shine plane-polarized light through a solution of (S)-alanine,
you will find that the light is rotated to the right. A solution of (R)-
alanine rotates plane-polarized light to the left (same magnitute but
opposite direction). Racemic alanine, on the other hand, lets the light
pass unrotated.
Different interaction (Reactivity) with other chiral molecules.
 Tutorial

f. What will be e.e. for the above solutions.

Some physical properties of the stereoisomers of tartaric acid
• The above pair of diastereoisomers are chiral because they don’t
have plane of symmetry.
Converting enantiomers and diastereoisomers
 To go form one enantiomer to another both steriogenic
centers are inverted.

 To go form one diastereoisomers to another only one of the

two is inverted.
Examples
 Identical, Enantiomers or
Diastereomers?
H CH2CH3
a) Br CH3 & H CH3

CH2CH3 Br

CH3
HO H
b) CH3 H NH2
H C C &
CH3 NH2 H OH

CH3
 Tartaric Acids
R,R S,S
CO2H CO2H

H OH HO H

HO H H OH

CO2H CO2H
R,S S,R
CO2H CO2H

H OH HO H

H OH HO H

CO2H CO2H
Meso compound
• Compounds that contain stereogenic center but
achiral are called Meso compound.
• The best way to identify a meso compound is to prove
that it is superimposable with its mirror image.
However, a quick test is to see if it contains a plane of
symmetry:
 Tartaric Acids
R,R S,S
CO2H CO2H

H OH HO H

HO H H OH

CO2H CO2H
R,S S,R
CO2H CO2H

H OH HO H

H OH HO H

CO2H CO2H