The conformation of simple alkenes can be considered

by beginning with propene.

There are two families of conformations available to

terminal alkenes: eclipsed and bisected conformations,
as shown below for propene. The eclipsed conformation
is preferred by about 2 kcal/mol and represents a barrier
to rotation of the methyl group.
A simple way to relate the propene rotational barrier to
that of ethane is to regard the pi bond as a “banana
bond” The bisected conformation of propene is then seen
to correspond to the eclipsed conformation of ethane,
while the more stable eclipsed conformation corresponds
to the staggered conformation of ethane.
1
The conformation of propene is influenced by
hyperconjugation. The methyl substituent has an overall
stabilizing effect (2.7 kcal) on the double bond, as can
be concluded from the less negative heat of hydrogenation
compared to ethene.
Computational approaches can provide an indication of the
magnitude of the interaction. The computation also shows a
shortening

3
With more highly substituted terminal alkenes,
additional conformations are available, as indicated for
1-butene. Conformations A and B are of the eclipsed
type, whereas C and D are bisected. It has been
determined by microwave spectroscopy that the eclipsed
conformations are more stable than the bisected ones
and that B is about 0.15 kcal more stable than A.

4
Further substitution can introduce van der Waals
repulsions that influence conformational equilibria. For
example, methyl substitution at C(2), as in 2-methyl-1-
butene, introduces a methyl-methyl gauche interaction
in the conformation analogous to B, with the result that
in 2-methyl-1-butene the two eclipsed conformations are
of approximately equal energy.

5
Increasing the size of the group at C(3) increases the preference
for the eclipsed conformation analogous to B at the expense of A.
4,4-Dimethyl-1-pentene exists mainly in the hydrogen-eclipsed
conformation

This interaction is an example of 1,3-allylic strain. This type of

steric strain arises in eclipsed conformations when substituents on
the double bond and the C(3) group, which are coplanar, are large
enough to create a nonbonded repulsion. The conformation of
alkenes is an important facet with regard to the stereoselectivity of
addition reactions of alkenes.

6
Allylic strain (also known as A1,3 strain, 1,3-allylic strain,
or A-strain) in organic chemistry is a type of strain energy
resulting from the interaction between a substituent on one
end of an olefin with an allylic substituent on the other end

7
The preferred conformations of carbonyl compounds, like 1-
alkenes, are eclipsed rather than bisected, as shown below for
ethanal and propanal. The barrier for methyl group rotation
in ethanal is 1.17 kcal/mol. Detailed analysis has indicated
that small adjustments in molecular geometry, including
sigma-bond lengthening, must be taken into account to
quantitatively analyze the barrier. In propanal, it is the
methyl group, rather than the hydrogen, that is eclipsed with
the carbonyl group in the most stable conformation. The
difference in the two eclipsed conformations has been
determined by microwave spectroscopy to be 0.9 kcal/mol. A
number of other aldehydes have been studied by NMR and
found to have similar rotameric compositions. When the
alkyl substituent becomes too sterically demanding, the
hydrogen-eclipsed conformation becomes more stable. This is
the case with 3,3-dimethylbutanal. 8
Ketones also favor eclipsed conformations. The preference is for
the rotamer in which the alkyl group, rather than a hydrogen, is
eclipsed with the carbonyl group because this conformation allows
the two alkyl groups to be anti rather than gauche with respect to
the other carbonyl substituent.

9
Conformations of Cyclohexane Derivatives
History

The conformational analysis of six-membered ring

compounds is particularly well developed. Cyclohexane
and its derivatives lend themselves to thorough analysis
because they are characterized by a small number of
energy minima. The most stable conformations are
separated by barriers that are somewhat higher and
more easily measured than rotational barriers in acyclic
compounds or other ring systems. The most stable
conformation of cyclohexane is the chair.

10
11
12
Two nonchair conformations of cyclohexane that have
normal bond angles and bond lengths are the twist and
the boat, both of which are less stable than the chair. A
direct measurement of the chair-twist energy difference
has been made using low-temperature IR spectroscopy.
The chair was determined to be 5.5 kcal/mol lower in
energy than the twist. The twist and the boat
conformations are more flexible than the chair, but are
destabilized by torsional strain, as the bonds along the
“sides” of the boat are eclipsed. In addition, the boat
conformation is further destabilized by a van der Waals
repulsion between the “flagpole” hydrogens. Both
this van der Waals repulsion and the torsional strain
are somewhat reduced in the twist conformation.
13
14
Boat Conformation
16
17
18
19
Equatorial Conformation is Preferred
Axial Methyl group is Gauche to C3 in the ring
Equatorial Methyl Group is Anti to C3 in the ring
The Conformations of Cyclohexane
and Their Energies
Energy differences between conformations of substituted
cyclohexanes can be measured by several methods, as can the
kinetics of the ring inversion processes. NMR spectroscopy is
especially valuable for both thermodynamic and kinetic studies.
Depending on the rate of the process, the difference in chemical
shift between the two sites and the field strength of the
spectrometer, the observed spectrum will be either a weighted
average spectrum (rapid site exchange, k>105sec−1) or a
superposition of the spectra of the two conformers reflecting the
equilibrium composition (slow site exchange, k< 103sec−1). At
intermediate rates of exchange, broadened spectra are observed.
Analysis of the temperature dependence of the spectra can
provide the activation parameters for the conformational process.
Figure 2.14 illustrates the change in appearance of a simple
spectrum. For substituted cyclohexanes, the slow-exchange
condition is met at temperatures below about −50C. Data for the
24
half-life for conformational equilibration of
25
26
27
28
29
30
31
32
33
34
35
The decalin (decahydronaphthalene) ring provides another
important system for the study of conformational effects in
cyclohexane rings. Equilibration of the cis and trans isomers
favors the trans isomer by about 2.8 kcal/mol. Note that this
represents a change in configuration, not conformation. The
energy difference can be analyzed by noting that the cis
isomer has an inter-ring gauche-butane interaction that is not
present in the trans isomer. There are also cross-ring
interactions between the axial hydrogens on the concave
surface of the molecule.

36
37
38
39
40
41
42
 tert-Butylcyclohexane
C(CH3)3

C(CH3)3

Less than 0.01% Greater than 99.99%

• Crowding is more pronounced with a "bulky" substituent

such as tert-butyl.
• tert-Butyl is highly branched.