Axial Chirality
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Axial Chirality in Systems Lacking Chiral
Centres
• Axial chirality is the sense of chirality in a system that
lacks a plane of symmetry but has no chiral centres.
• Instead of chiral centres, axially chiral systems have an
axis of chirality (chiral axis).
• A chiral axis is a line about which a set of four groups is
held in a non-planar arrangement resulting in non-
superimposable mirror images.
• Axial chirality is encountered in allenes and ortho-
4:06 PM substituted biphenyls. 2
What are Allenes?
Definition
• Allenes are compounds with two or more double bonds
side-by-side.
• Such bonds are called cumulated double bonds.
• Note that cumulated double bonds are distinct and
different from conjugated double bonds that comprise of
alternate double-single-double bonds.
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Structure of Allenes
The Facts Revisited
• The central carbon of an allene forms two sigma bonds
and two pi bonds. The central carbon is sp-hybridized,
while the two terminal carbons are sp2-hybridized.
• The planes of the two π-bonds attached to the central
carbon are perpendicular (orthogonal) to each other.
• The geometry of the π-bonds causes the groups
attached to the end carbons to lie in orthogonal planes.
• The bond angle formed by the three carbons is 180°,
indicating a linear geometry for the carbons of allene.
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Structure of Allene
The Geometry and Symmetry
• Since the bond angle formed by the three carbons is
180°, the cumulated carbons of the double bonds of the
allene are in a linear geometry.
• For allenes with four identical substituents, there exist
two twofold axes of rotation through the center carbon,
inclined at 45° to the CH2 planes at either end of the
molecule.
• A mirror plane passes through both CH2 planes.
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Axially Chiral Systems
Chirality of Allenes: The Genesis
• Since the geometry of the cumulated π-bonds causes
the groups at the terminal carbons to lie in
perpendicular planes, allenes that are unsymmetrically
substituted on both terminals are chiral.
• Note that allenes with odd numbers of cumulated
double bonds are not chiral; only those with even
numbers have a potential to be chiral.
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Chirality of Allenes
Specific Rotations
• Since allenes with different substituents attached to the
end carbons form non-superimposable mirror images,
they show optical activities even though they do not
have a chiral carbon.
• How can we assign configurations to the optically active
4:06 PM allenes? 7
Chirality of Allenes
Configurations of Axially Chiral Systems
• The configurations in axially chiral systems are
specified using Ra and Sa or P (plus) and M (minus).
The subscript “a” refers to “axial” chirality.
Sequence Rules
• The CIP rules are used to assign priority to the end
groups, but with one addition: That the “near” groups
have a higher priority over “far” groups. The two "near"
and two "far" groups on the chiral axis are ranked (a, b,
c and d).
Viewing Rule
• The chiral axis is viewed end-on (along the chiral axis)
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and the sense of configuration determined.
Chirality of Allenes
Configurations of Axially Chiral Systems
• The model below shows the side views and
representations of the allene along the chiral axis.
• These side views can be used to determine the
configuration around the chiral axis of the allene.
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Configurations of Chiral Allenes
Assigning Priority to Substituents
• To determine the sense of configuration, assign priority
to the substituents on each of the terminal carbons of
the allene along the chiral axis.
• You may use a (highest priority) to d (lowest priority).
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Configurations of Chiral Allenes
Determining the Sense of Rotation (Ra vs Sa)
• The sense of rotation is determined starting with the
end of the allene that is “near”, then finishing with the
end that is “far”.
• For the far end, only the group of higher priority is
considered.
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Configurations of Chiral Allenes
Determining the Sense of Rotation (P vs M)
• The sense of rotation is determined by looking only at
the high priority substituents starting with the “near” end
of the allene along the chiral axis, then finishing with the
“far” end.
• A clockwise rotation is P (plus) and an anticlockwise
rotation is M (minus).
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Axially Chiral Systems
Biphenyl Systems
• Biphenyls are compounds in which a phenyl ring is
connected to another through a central σ-bond.
• In unsubstituted biphenyl, there is sufficient amount of
freedom of rotation around the central single bond to
allow for free interconversion between the various
conformers or rotamers to the extent that the various
rotamers can not exist independently of each other.
• The same phenomenon also applies to other biaryl
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systems. 13
Axially Chiral Systems
Biphenyl Systems (Atropisomerism)
• Biphenyls with large substituents at the ortho positions
on either side of the central σ-bond experience
restricted rotation on the bond due to steric hindrance.
• If the substituents are different, a chiral compound
existing as a pair of enantiomers called atropisomers is
obtained.
• The enantiomers can be made racemic by heating. The
free energy required is in the range of 42 - 210 kJ/mole.
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Axially Chiral Systems
Atropisomerism
• Atropisomers are stereoisomers that can be
interconverted by rotation about single bonds but for
which the barrier to rotation is large enough that the
stereoisomers do not interconvert readily at room
temperature and can exist independently.
• Polynuclear aromatic systems such as binol (1,1’-Bi-2-
naphthol) also exist as atropisomers (enantiomers).
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Chirality in Biaryl Systems
Assigning Configurations to Atropisomers
• Configurations of atropisomers are assigned in a similar
fashion as those of chiral allenes using Ra and Sa or P
(plus) and M (minus).
• By generating appropriate models of each atropisomer,
the sense of configuration can be determined.
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Chirality in Biaryl Systems
Assigning Configurations to Atropisomers (Ra vs Sa)
• By generating appropriate models of each atropisomer,
the sense of configuration can be determined.
• The two atropisomers are nonsuperimposable mirror
images and therefore enantiomers.
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Chirality in Biaryl Systems
Assigning Configurations to Atropisomers (P vs M)
• Using appropriate models of each atropisomer, the
sense of configuration (P/M) can be determined.
• Try to draw the LHS and RHS views of each
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atropisomer and determine their configurations. 18
Assignment
Configurations of Axially Chiral Systems
• Determine the configurations of the following axially
chiral systems using both the Ra/Sa and P/M notations.
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Assignment
Configurations of Axially Chiral Systems
• Configurations of afloqualone by Ra/Sa and P/M
notations.
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