CHM 124 Stereochemistry Defined

Stereochemistry is the study of the three-dimensional structure of molecules. The cis and trans isomers
are forms of stereoisomers, differing structurally only in the location of the atoms of the molecule in
three-dimensional space. Such stereoisomers can have different physical and chemical properties. For
example, the cis and trans isomers of butenedioic acid show vast differences in their physical and
chemical properties.

Stereochemistry is of particular interest to biochemists because the reactivity and toxicity of molecules
change with their stereochemistry. Most body reactions are stereospecific, meaning that receptor sites
on cells accept only molecules with specific spatial arrangements of their atoms. Other configurations
of the same chemical either will not react or may be toxic to the living being.

There are other types of stereoisomers in addition to the cis and trans arrangements of atoms. To
understand these other isomers, you must first understand the three-dimensional structures of the
molecules.

Optical Activity

The stereochemistry of molecules has its roots in the work of the nineteenth-century French physicist
Jean Biot. Biot was studying the nature of plane-polarized light (Figure 1 ) when he discovered that
solutions of some organic compounds caused polarized light to rotate. Compounds with this property
are called optically active, and the amount and direction of rotation can be determined with a
polarimeter (Figure 2 ).

Figure 1

1
 Figure 2

White light consists of electromagnetic waves oscillating in an infinite number of planes at right angles
to the direction of light travel. Plane-polarized light is ordinary white light that has passed through a
polarizer. A polarizer is a filter that blocks the light waves in all planes but one. A common example
is a pair of Polaroid sunglasses, which prevent glare by polarizing sunlight. Figure 1 illustrates the
concept of plane-polarized light.

Figure 2 shows how the optical activity of a compound is measured in a polarimeter.

In 1849, while doing recrystallization experiments with tartaric acid salts, Louis Pasteur isolated two
distinct kinds of crystals. Upon microscopic examination, he discovered the crystals were
nonsuperimposable mirror images of each other. Pasteur was able to separate the different crystals into
two piles. Solutions of the pure samples of each kind of crystal showed optical activity. The angle of
rotation (α) in a polarimeter was the same for both solutions, but the directions of rotation were
opposite. A solution of the original mixture of crystals showed no optical activity. The crystalline
structure of the tartrate salt crystals is illustrated in Figure 3

Figure 3
As you can see, the crystals are nonsuperimposable, having the same relationship as a right hand to a
left hand. Such opposite configurations are called enantiomers; thus, the two forms of tartrate crystals
are enantiomers of each other.

Optical purity. A collection of molecules of one enantiomer is said to be optically pure, while a 1:1
mixture of two enantiomers is a racemic mixture. Between these two extremes, there can be an
infinite number of mixtures containing various ratios of two enantiomers. Such chemical mixtures have
a specified optical purity. The optical purity of a mixture of enantiomers is defined as the ratio of the
rotation of the mixture to the rotation of the pure enantiomers.