Stereochemistry of Alkanes and Cycloalkanes

Conformation of ethane:
Rotation is possible around C-C

Different arrangements of atoms that can be converted into one another

by rotation about single bonds are called conformations
Each specific structure is called a conformer or conformational isomer
Conformational isomers can be represented in two ways:
Newman representation
Sawhorse representation

H
H

H
H

H
C
H

Conformational isomers cannot be isolated (fast interconversion)

Staggered

Eclipsed

Staggered

Intermediate geometries are called skew conformations

The angle between C-H bonds on front and back carbons is called the
dihedral angle: (0 to 360).
H-H eclipsed interaction = 4 kJ/mol or 1 kcal/mol

Conformations of propane and butane

Propane.
staggered
CH3
H
H

eclipsed
1.0 kcal/mole HH

CH3
H

1.4 kcal/mole

H
H

HH
1.0 kcal/mole

Eclipsed conformation: 2 (H-H = 1.0 kcal/mol) = 2.0 kcal/mol

H-CH3 = 1.4 kcal/mol = 1.4
Total = 3.4 kcal/mol

n-Butane
Staggered conformations have lower torsional energy and are
more stable than eclipsed conformation.

CH3
H

anti

H
CH3
CH 3
H

H
H

eclipsed

H 3C H
H
H

gauche
H

CH3
CH3

eclipsed

H
H

H
H

H3C CH3

The most favorable conformation for any alkane is the one in which
the C-C bonds have staggered arrangements and in which large
substituents are arranged anti to each other.
Energy Cost
Interaction
Cause
kJ/mole kcal/mol
HH eclipsed
Torsional strain
4.0
1.0
HCH 3 eclipsed
Mostly Torsional strain
6.0
1.4
CH 3 CH 3 eclipsed Torsional plus Steric strain
11
2.5
CH 3 CH 3 gauche
Steric strain
3.8
0.9
At room temperature, rotation around bonds occur rapidly, so all
conformers are present. At any given in stant there is greater % of the
more stable isomer.

Conformation and Stability of Cycloalkanes: The

Baeyer Strain theory
Baeyer suggested that, since carbon prefers tetrahedral
geometry (~109), ring sizes other than 5 and 6 may be too
strained to exist.

109
49
60
Cyclopropane

19
90

108

Cyclobutane

Cyclopentane

Total energy of a compound - energy of a strain-free reference compound = extra

energy in the compound due to strain.
Heat of combustion or energy released when a compound burns with oxygen
helps to determine energy strain.
The more strained the compound the more heat of combustion (more energy is
released). Cyclohexane is strain free. See figure 4.8 and 4.9.
Cycloalkanes adopt their minimum energy conformations for a combination of
three reasons:
Angle strain, strain due to expansion or compression of bond angles
Torsional strain, strain due to eclipsing of bonds in neighboring atoms
(bonding electrons repel each other)
Steric strain, strain due to repulsive interactions when atoms are too close

Cyclopropane
Poor overlap of atomic orbitals in the formation of C-C bonds.

C
C

C
C

109
typical C-C bond

bent cyclopropane bond

C-C-C bond angle can not be 109.5, but instead 60(angle strain = 49.5).
There is less overlap therefore, the bond is weaker than the usual C-C bond.
Cyclopropane has bent bonds.
Total strain energy for cyclopropane = 114.9 kJ/mol

Cyclobutane

Less angle strain than cyclopropane, but more torsional

strain.
Total strain energy 110.4 kJ/mol
Is not flat, see figure 4.12
Almost eclipsed

Cyclopentane

Internal angles = 108 (1 angle strain)

Adopts a puckered out-of-plane conformation
Total strain energy = 26.0 kJ/mol (from
torsional strain), fig 4.13

Cyclohexane
All angles = 109.5
There are different conformations:

chair

boat

twist-boat

The chair form is the most stable conformation for cyclohexane.

How to draw a chair conformation?
Six axial bonds, one on each carbon, are parallel and alternate up and
down

Six equatorial bonds, one on each carbon, come in three sets of two
Parallel lines.

Chair cyclohexane has no torsional strain

H (axial)
6

H (equatorial)
H

2
6
1

newman projection

staggered ethane

Chair cyclohexanes can rapidly interconvert (ring flip)

CH3
1
H
H 3C
1
H

axial
equatorial

becomes equatorial
becomes axial

A substituent is always more stable in an equatorial position than in

an axial position
H
6

CH3

H
4

CH3

H
2

H
equatorial CH3

axial CH3

1,3-diaxial interaction

Disubstituted Cyclohexanes
Monosubstituted cyclohexanes usually have the substituent in equatorial
position.
Disubstituted cyclohexanes
more complex situation: Steric effect
Example: Cis-1,2-Dimethylcyclohexane
CH3

CH3
H

CH3

CH3

CH3

H
H

ring
flip

CH

Two CH3-H diaxial interactions = (2x3.8) 7.6 kJ/mol

One gauche interaction
= 3.8 kJ/mol
Total strain
= 11.4 kJ/mol

Trans-1,2-Dimethylcyclohexane
H

CH3
CH3
H
CH3

CH3
CH3
H

H
ring
flip

H
I

CH3
II

(I) One gauche interaction = 3.8 kJ/mol

(II) Four CH3-H diaxial interactions = 15.2 kJ/mol

Boat cyclohexane:
Free of angle strain
Less stable than chair conformation (steric and torsional strain)
1
H

6
H

H 2C

H2
C

H H

3
H

Note eclipsing and Steric strain from 1,4 interaction

Total strain = 29 kJ/mol

Twist-boat conformation = 23 kJ/mol