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BASIC CONCEPT OF STEREO CHEMISTRY

BASIC CONCEPTS

Isomers Constitutional Isomers Stereoisomers Enantiomers Diastereomers Chiral and Achiral Meso Compounds Optical Activity R and S Nomenclature

ISOMERS

Any of two or more substances that are composed of the same elements in the same proportions but differ in properties because of differences in the arrangement of atoms. i.e. A simple example of isomerism is given formula C3H8O .

Constitutional Isomers

Structural Isomers are molecules which have the same molecular formula but have different connectivity's . Three categories of constitutional isomers are skeletal, positional, and functional isomers. In skeletal isomerism, or chain isomerism, components of the (usually carbon) skeleton are distinctly re-ordered to create different structures. For example 3-methylpentane is a chain isomer of 2methylpentane

In position isomerism a functional group changes position on the chain. In the diagram, pentane-2-ol has become pentan-3-ol

In functional group isomerism a functional group splits up and becomes a different group. Here is an example of functional group isomerism: take cyclohexane, C6H12 and hex-1-ene, also C6H12. These two are considered functional group isomers because cyclohexane is an alkane and hex-1ene is an alkene. Both must have the same molecular formula.

Stereoisomers

Stereoisomers are molecules with identical connectivity but different spatial arrangements of their constituent atoms that cannot be interconverted by bond rotation.

Enantiomers

Either of two stereoisomers that are mirror images of one another but cannot be superimposed on one another and that rotate the plane of polarized light in opposite directions. Enantiomers usually behave the same chemically but differ in optical behavior and sometimes in how quickly they react with other enantiomers. Also called optical isomer.

The two enantiomers are:

Diastereomers

Diastereomers are stereoisomers that are not enantiomers; that is, they are distinct molecules with the same structural arrangement of atoms that are nonsuperimposible, non-mirror images of each other.

(2S,3S)-tartaric acid

(2R,3R)-tartaric acid

(2R,3S)-tartaric acid

In tartaric acid, both of the central carbon atoms are stereogenic centers. Thus, they both must be assigned R or S configurations according to the CahnIngoldPrelog system. The first two molecules shown above, (2S,3S)tartaric acid and (2R,3R)-tartaric acid, are clearly enantiomers of each other since they are mirror images. But what about the third molecule, (2R,3S)-tartaric acid? It is clearly distinct from the first two, yet the same atoms are bonded to each other. It is also very clearly not a mirror image of either of the first two. Thus, as a nonsuperimposible, non-mirror image with the same arrangement of atoms, (2R,3S)-two molecules.

Chiral and Achiral

Chiral objects have nonsuperimposable mirror images and form a pair of enantiomers. Achiral objects have mirror images that are identical (superimposable). The following objects were tested: snail shell (chiral), pencil (achiral), glove (chiral), hand (chiral), a carbon atom with four different substituents (chiral), a carbon atom with three different substituents (achiral)

Optical ActivityYour left hand is the mirror image of your right.

The two hands are "non-superimposable mirror images". Molecules that are "non-superimposable mirror images" are optically active. We say the molecules are "chiral". We say the pair of molecules is an "enantiomeric pair".

Meso Compounds

A compound with two chirality centers where there is the same set of four groups at each chirality center, the combination where the four groups are arranged such that the centers are mirror images of each other (i.e. where the molecule has an internal mirror plane) is a meso compound.

Example of Meso compound

For example consider 2,3-dichlorobutane. There are two chirality centers (C2 and C3), each with -H, -Cl, -CH3 and the other -CHClCH3 groups attached. Since there are two chirality centers, then, at least in principle, there are 4 possible permutations (R,R), (R,S), (S,R) and (S,S) If we look at the (R,S) and (S,R) as drawn above, these two structures are actually the same thing because they are superimposable. This structure is the meso isomer.

Optical Activity

Optical activity is the ability of a chiral molecule to rotate the plane of plane-polairzed light. It is measured using a polarimeter, which consists of a light source, polarizing lens, sample tube and analyzing lens.

Simple substances which show optical isomerism exist as two isomers known as enantiomers. A solution of one enantiomer rotates the plane of polarisation in a clockwise direction. This enantiomer is known as the (+) form. For example, one of the optical isomers (enantiomers) of the amino acid alanine is known as (+)alanine. A solution of the other enantiomer rotates the plane of polarisation in an anti-clockwise direction. This enantiomer is known as the (-) form. So the other enantiomer of alanine is known as or (-)alanine. If the solutions are equally concentrated the amount of rotation caused by the two isomers is exactly the same but in opposite directions. When optically active substances are made in the lab, they often occur as a 50/50 mixture of the two enantiomers. This is known as a racemic mixture or racemate. It has no effect on plane polarised light.

R and S Nomenclature

Since two enantiomers are different compounds, we will need to have nomenclature which distinguishes them from each other. The convention which is used is called the (R,S) system because one enantiomer is assinged as the R enantiomer and the other as the S enantiomer. What are the rules which govern which is which??

Priorities are assigned to each of the four different groups attached to a given stereogenic center (one through four, one being the group of highest priority). (It should be understood that each stereogenic center has to be treated separately.) Orient the molecule so that the group of priority four (lowest priority) points away from the observer. Draw a circular arrow from the group of first priority to the group of second priority. If this circular motion is clockwise, the enantiomer is the R enantiomer. If it is counterclockwise, it is the S enantiomer.

The Sequence Rule for Assignment of Configurations to Chiral Centers Assign sequence priorities to the four substituents by looking at the atoms attached directly to the chiral center. 1. The higher the atomic number of the immediate substituent atom, the higher the priority. For example, H < C < N < O < Cl. (Different isotopes of the same element are assigned a priority according to their atomic mass.) 2. If two substituents have the same immediate substituent atom, evaluate atoms progressively further away from the chiral center until a difference is found. For example, CH3 < C2H5 < ClCH2 < BrCH2 < CH3O. 3. If double or triple bonded groups are encountered as substituents, they are treated as an equivalent set of singlebonded atoms. For example, C2H5 < CH2=CH < HCC

The Viewing Rule Once the relative priorities of the four substituents have been determined, the chiral center must be viewed from the side opposite the lowest priority group. If we number the substituent groups from 1 to 4, with 1 being the highest and 4 the lowest in priority sequence, the two enantiomeric configurations are shown in the following diagram along with a viewers eye on the side opposite substituent #4.

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