Chirality

Chiral Centres
A chiral centre (sometimes known as an asymmetric carbon) is a carbon atom with 4 different groups
attached to it. For example:












The carbon in the middle is the chiral centre as it has 4 different groups attached to it: a hydrogen, a CH3,
an OH and a CH2CH3 group.

when looking for a chiral centre, a quick tip is to look for the carbon atoms with a hydrogen attached,
as most chiral centres have a hydrogen as one of the four groups. Not every single example but most.


There are many different types of molecules with chiral centres. For example:




chiral centre
chiral centre

Carbon atoms without chiral centres:
Ignore any double bonds. Ignore benzene. Ignore symmetrical cyclic molecules.

some molecules might have more than one chiral centre. The molecule below has 8!

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Optical isomers
Like geometric isomers at AS, optical isomers are an example of stereoisomerism, so its all about the
spatial arrangement of atoms again.

But with optical isomers we are looking at chiral centres and not double bonds. So a molecule with a
chiral centre will exist as a pair of optical isomers.

Mirror Images
Optical isomers exist as two halves. If you have a chiral molecule (one with a chiral centre) and you are
asked to draw the other isomer, all you have to do is draw the mirror image of the molecule.



The easiest way to do this is by using the tetrahedral notation:






The dashed line and the thick black line are to show the molecule in three dimensions i.e. the dashed
line is going into the plane of the paper and the black line is coming out.

It doesnt matter which groups are on each bond.

Below I drew out the original molecule again then simply drew the mirror image of it. The line down the
middle represents a mirror:

I drew the CH2CH3 group inverted in the right hand structure but you dont have to do this. You could
write it out CH2CH3 if you prefer. Its more about making sure the tetrahedral structure has been
inverted.

In this branch of chemistry, they call the isomers enantiomers and the two structures are said to be non-
superimposable mirror images of each other.

So if they ask for a definition of optical isomers:


two non-superimposable mirror images



Non-superimposable just means there is no way that you can overlay the two isomers on top of each
other and get an exact match (they may appear identical but theyre not).

Its a bit like trying to overlay your right hand on top of your left hand. Both hands have a thumb and 4
fingers but you cant place the thumbs on top of each other if both palms are facing down.

Optical Activity
The amount that chiral molecules rotate plane polarized light is known as optical activity. The molecules
are placed in a machine and plane polarized light is shone at them. The result is an angle from the
machine.

If there is no chiral centre, then NO rotation of plane polarized light occurs, and the molecule is said to be
optically inactive.




optical activity is the only way you can distinguish between optical isomers


The molecules are so similar that physical properties like melting point, density etc will all be the same.
Even using spectroscopic techniques would be very difficult/impossible to tell them apart.

Racemic Mixtures
An exam favourite is to ask about racemic mixtures. This is when you have a molecule with a chiral centre
but it is optically inactive, which goes against what we have just said!


a racemic mixture contains equal amounts of both enantiomers (50:50 mixture)



As a racemic mixture has equal amounts of both isomers, the optical activities cancel out. For example,
one isomer might rotate the light by +10 degrees and the other isomer by -10 degrees. The overall value
from the machine is 0 degrees. It then appears that they are not optically active or have chiral centre.

Im guessing you want to know why, which also happens to be an exam favourite. It all goes back to how
the molecules are made in the first place.

Racemic mixtures result from either nucleophilic addition to ketones or aldehydes. Or a carbocation
intermediate such as in a SN1 mechanism. Below is an example of nucleophilic attack on a carbonyl group.







The key point is that the carbonyl group is planar or flat. This means that the nucleophile can attack from
above or below the carbonyl group, which results in the formation of the two enantiomers.

The nucleophile has a 50:50 chance of attacking from above or below the carbonyl group, and therefore a
50:50 mix of isomers is produced.

dont worry about which enantiomer comes from the nucleophile attacking from above and which
comes from attacking from below, that doesnt matter.


SN1 versus SN2

Below is the mechanism for the SN1 mechanism. In step 2 we have a carbocation intermediate, which is
planar (flat). The CN- nucleophile can therefore attack from above or below resulting in a 50:50 mixture
of isomers.



















The SN2 mechanism does not involve an intermediate, therefore only one isomer is obtained.

the product is still chiral but note the inversion in the tetrahedral structure. It is sometimes referred
to as an umbrella being blown inside out when you compare the product to the starting haloalkane.

the middle stricture is not an intermediate. It is a transition state. A hypothetical structure that
shows simultaneous bond breaking and making.