Various Representations of Molecules

Flying-wedge formula

Sawhorse formula
3D Image
Ethane

Newman Projection

Fischer Projection
 Fischer Representation

Methane

3D Structure Fisher projection – 2D

1
1

2
= 3 4 =
3
4
2

view Fischer Projection

Perspective drawing
Or Flying-wedge formula
Fischer Representation
 Rules for Fischer Projection
1. Cannot lift projection out of plane of paper.
2. Can be rotated in plane of paper only by 180
3. 2 pairs of substituents can be exchanged.
Remember - Exchange of only 1 pair gives enantiomer!

Br CH3 CH2CH3
R R R
CH3 CH2CH3 Br H H Br

H CH2CH3 CH3

4. One atom can be fixed and the other 3 can be rotated

(DO NOT change the sequence of 3 you are rotating)
Interconverting Representations
 Small Activity

Convert the above structure to flying wedge

You can work in pairs or groups!

 R/S Assignment in Fischer Projection
• Remember “Very Good” = “Vertical is Good”!

• Assign priority 1-4.

• Find direction from 1-3 and use R/S chirality rule

• If substituent 4 is on vertical line, it’s correct R/S

nomenclature

• If no. 4 substituent is not on vertical line, the answer

is wrong and you write opposite!
 Examples

S
R S
R
R S
R

2R, 3R 2S, 3R, 4R

You can practice assigning the absolute configuration

of all the stereocentres of D-glucose and other sugars
as homework
 Small Activity

R
S
S R
R R

You can check your answer to this question by

assigning the absolute configuration of both
structures
 2 or More Chiral Centres
• Maximum number of isomers is 2n, where n
= the number of chiral carbons.

• Then can be enantiomers, diastereomers, or

meso isomers

Enantiomers have opposite configurations at

each corresponding chiral carbon.

Diastereomers have some matching, some

opposite configurations.

Meso compounds have internal mirror planes

 Fischer’s D and L Nomenclature
Glyceraldehyde : simplest chiral sugar (carbohydrate)

D-(+)-glyceraldehyde L-(-)-glyceraldehyde

An enantiomerically pure compound related to the

configuration of

D-glyceraldehyde D

L-glyceraldehyde L
 Rules for Determining D- and L-
Writing Fischer projection

• Write the longest C chain vertically

• Most oxidized group to be placed

on top

Determining configuration

• Consider the bottom-most chiral

centre

• If X group on the right – D, if on the

left - L
 Optical Families
CHO CHO

H * OH HO * H L-(-)-glyceraldehyde
D-(+)-glyceraldehyde
CH2OH CH2OH

CHO CHO

(CHOH)n (CHOH)n
D-sugars L-sugars
H * OH HO H

CH2OH CH2OH

D-amino acids L-amino acids

CO2H CO2H

H NH2 H2N H

R R

Remember - NO direct relationship between R/S and D/L

 Axial Chirality
These molecules are chiral without having chiral centres

These molecules are axially chiral (axial asymmetry)

arises due to restricted rotation around the C-C bond

They need not have 4 different substituents for chirality!

2 is enough!
 Atropisomerism
Chirality due to restricted rotation around the bond connecting
the two phenyl rings – also referred to as Atropisomerism

Why are two different substituents enough?

 Axial Chirality – Another Example

Cl
Cl Cl
Cl
The three Cs form the axis
The perpendicular planes
contain substituents
Allene in a Box

Axis of symmetry in allene

 Examples of Axial Chirality

Alkylidine cyclohexane

Adamantanes

Spiranes
 Assigning Absolute Configuration
CIP Rules – Subrule 0 comes in play!
Nearer end of an axis or plane precedes the farther end
(proximity ride)

• The molecule is viewed along the chiral axis;

• Near ligands take precedence over far;
• The ligand of lowest priority is ignored

Note: Here H can be on the vertical or horizontal line . Both are good
 Examples

Try viewing the molecule from right and doing the same exercise.
Does it change your answer? NO
More Examples
 Summary
Isomers – Different molecules with the same molecular formula
Bonding connectivity same?
No Yes
Constitutional Stereoisomers
Isomers
Mirror images?
Yes No
Enantiomers Diastereomers

Meso compounds They have a plane of symmetry in the molecule

 Learning Outcomes

At the end of this module you should be able to….

• Recognize the elements of symmetry present in a
molecule or object and determine if it is chiral
• Differentiate between various types of stereoisomers
• Represent 3D molecules using appropriate 2D
representations
• Assign the absolute configuration of chiral centers and
molecules with axial chirality