Allenes and Biphenyls:
There are compounds with nonsuperimposable mirror images but donot have stereocentre,
then to predict the stereochemistry of such compounds it becomes necessary to focus our
attention on other aspects of the molecule. Thus, the presence of stereocentre is not a
necessary and sufficient condition for molecular dissymmetry. The overall chirality of a molecule
can be categorised in to three elements; i) stereocentres; ii) stereoaxes; and iii) stereoplanes,
one other element of chirality is still there and called helicity.
Chirality due to axes (Axial chirality): Such type of chirality is produced in a molecule when
there is no chiral centre present in the molecule. When four atoms/groups attached to a central
atom are located on the corners of tetrahedron the central atom is termed as chiral centre. If
the chiral centre is replaced by a linear grouping like C-C or C=C=C, the tetrahedron geometry
get extended along the axis of the grouping and thus generates a chiral axis. Depending on the
nature of groups attached with the carbon atoms, some examples of molecules with chiral axis
are allenes and biphenyls.
Allenes: Allenes are compounds with two or more double bonds side-by-side. Such bonds are
called cumulated double bonds. The central carbon of allene forms two sigma bonds and two pi
bonds. The central carbon is sp-hybridized and the two terminal carbons are sp2-hybridized. The
two π-bonds attached to the central carbon are perpendicular to each other. The geometry of
the π-bonds causes the groups attached to the end carbon atoms to lie in perpendicular planes.
The bond angle formed by the three carbons is 180°, indicating linear geometry for the carbons
of allene.
Stereochemistry of Allenes: When three or more adjacent carbon atoms in a molecule are
bonded by double bonds, the compounds is called cumulene or said to have cumulative double
bonds. Allene is the simplest example of this class. Allenes are chiral and they have
nonsuperimposable mirror images and exist as enantiomers although they have no chiral centre.
An allene is said to be chiral if the two substituents at each end are different from each other (a≠ b).
Stereochemistry of Biphenyls:
Stereoisomers obtained due to the restricted rotation about carbon-carbon single bond are called
atropisomers and the phenomenon is called atropisomerism. Such compounds also have the
chirality due to the axis. Suitably substituted biphenyls exhibit enantiomerism due to the presence
of chiral axis. This enantiomerism arises due to atropisomerism i.e. restricted rotation around C-C
bond between two phenyl rings. This steric hindrance of substituents at ortho- position of the
each ring is responsible for such restricted rotation. To maintain the maximum stability, molecule
orients itself in such a manner so that both the ortho- substituted phenyl rings lie in different
plane.
Biphenyl shows the enantiomerism when the molecule has the following properties.
a) Each ring must be unsymmetrically substituted. Each of the rings should not contain
any kind of symmetry element.
b) Suitable substitution (at least one substitution) at ortho- position must be there at each
rings.
c) ortho- substituents must be larger in size (-Cl, -Br, -I, -COOH, -NO2, -NHCOCH3, -
SO3H, -R groups etc.).
The smaller groups at ortho- position make the compounds planar in nature and thus do not
exhibit atropisomerism.
