CONFORMATIONS OF ORGANIC

MOLECULES
 Sigma Bonds & Bond Rotation

 Two groups bonded by a single bond can undergo rotation about that bond with
respect to each other

● Conformations – temporary molecular shapes

result from a rotation about a single bond
● Conformer – each possible structure of
conformation
● Conformational analysis – analysis of energy
changes occur as a molecule undergoes
rotations about single bonds
Ch. 4 - 2
 Newman Projections

Me
H H Sawhorse formula

Cl OH
Et
Look from this
direction
H Me H H
combine Me H
Cl Et OH Cl Et
front carbon back carbon OH
Newman Projection

Ch. 4 - 3
 How to Do a Conformational Analysis

Look from this

direction f1 = 60o

a
H
f2 = 180o H
b
H staggered
confirmation
H H of ethane
c
H
Ch. 4 - 4
 60o 0o
CH3
CH3 CH3 CH3
CH3
180 o

CH3
anti gauche eclipsed

Ch. 4 - 5
Look from this
direction
f = 0o

HH
eclipsed
confirmation
H H of ethane
H H
Ch. 4 - 6
Ch. 4 - 7
 Conformational Analysis of
Butane
H Me
Me H H H

H Me H H
H Me
Sawhorse formula New Projection
formula

Ch. 4 - 8
 CH3
CH3 H CH3
H H
  CH3 H

H H H H H H
CH3 CH3 H H
anti conformer eclipsed conformer gauche conformer
(I) (II) (III)
(lowest energy)

= CH3 on front carbon 
rotates 60o clockwise

CH3 CH3
H CH3 H3C
 H CH3


H H H H H H
H CH3 H H H
eclipsed conformer gauche conformer eclipsed conformer
(VI) (V) (IV)
(highest energy)
Ch. 4 - 9
Ch. 4 - 10
Stereochemistry: Conformational
analysis of cyclohexane (Chair)
Stereochemistry: Conformational
analysis of cyclohexane (Boat)
Conformations of Cyclohexane:
The Chair & the Boat

6 4 2 3
3D 5

2 6 5
1 3 1 4
(chair form) (boat form)
(more stable) (less stable)

H 4
H H H
H H H H
3 5
6 2
5 3 2
4
6
H 1
H HH HH
1
H H
Ch. 4 - 13
 The boat conformer of cyclohexane is less stable (higher energy) than the chair
form due to
● Eclipsed conformation
● 1,4-flagpole interactions

1
H H 4

H H
H H
(eclipsed)

Ch. 4 - 14
 (twist boat)

 The twist boat conformation has a lower energy than the pure boat conformation,
but is not as stable as the chair conformation

Ch. 4 - 15
 Energy diagram

Ch. 4 - 16
Stereochemistry: Conformational analysis of
cyclohexane (Ring Flip and stability)
Stereochemistry: Conformational analysis of
cyclohexane (Ring Flip and stability)
 Substituted cyclohexane
● Two different chair forms

G
H
G

G H
(equatorial G) (axial G) G
(more stable) (less stable)
Ch. 4 - 19
 The chair conformation with axial G is less stable due to 1,3-diaxial interaction

1,3-diaxial interaction

H G
3 H
1 H

 The larger the G group, the more severe the 1,3-diaxial interaction and shifting the
equilibrium from the axial-G chair form to the equatorial-G chair form

Ch. 4 - 20
 G

(equatorial) (axial) G

At 25oC
G % of Equatorial % of Axial
F 60 40
CH3 95 5
Pr
i
97 3
t
Bu > 99.99 < 0.01 Ch. 4 - 21
 Substituted Cyclohexanes: Axial
& Equatorial Hydrogen Atoms
 Equatorial hydrogen atoms in chair form

H
H H
H H
H
 Axial hydrogen atoms in chair form

H H
H

H
H H
Ch. 4 - 22
 Which ones are chiral?

Br Br
Br
Br Br
Br
1 2 3