4.3 Diastereomers

Diastereomers are stereoisomers that are not related as object and mirror image and are not enantiomers. Unlike enatiomers which are mirror images of each other and non-sumperimposable, diastereomers are not mirror images of each other and non-superimposable. Diastereomers can have different physical properties and reactivity. They have different melting points and boiling points and different densities. They have two or more stereocenters.

Introduction

It is easy to mistake between diasteromers and enantiomers. For example, we have four steroisomers of 3-bromo-2-butanol. The four possible combination are SS, RR, SR and RS (Figure 1). One of the molecule is the enantiomer of its mirror image molecule and diasteromer of each of the other two molecule (SS is enantiomer of RR and diasteromer of RS and SR). SS's mirror image is RR and they are not superimposable, so they are enantiomers. RS and SR are not mirror image of SS and are not superimposable to each other, so they are diasteromers.

Figure 1

Diastereomers vs. Enantiomers vs. Meso Compounds

Tartaric acid, C₄H₆O_6, is an organic compound that can be found in grape, bananas, and in wine. The structures of tartaric acid itself is really interesting. Naturally, it is in the form of (R,R) stereocenters. Artificially, it can be in the meso form (R,S), which is achiral. R,R tartaric acid is enantiomer to is mirror image which is S,S tartaric acid and diasteromers to meso-tartaric acid (figure 2).

(R,R) and (S,S) tartaric acid have similar physical properties and reactivity. However, meso-tartaric acid have different physical properties and reactivity. For example, melting point of (R,R) & (S,S) tartaric is about 170 degree Celsius, and melting point of meso-tartaric acid is about 145 degree Celsius.

Figure 2

To identify meso, meso compound is superimposed on its mirror image, and has an internal plane that is symmetry (figure 3). Meso-tartaric acid is achiral and optically unactive.

Problems

Identify which of the following pair is enantiomers, diastereomers or meso compounds.

Answer

1. Diasteromers
2. Identical
3. Meso
4. Enantiomers

Outside Links

• http://www.sparknotes.com/chemistry/...section2.rhtml
• http://en.Wikipedia.org/wiki/Diastereomer
• http://en.Wikipedia.org/wiki/Tartaric_acid

4.3.1 Different Types of Isomers

4.3.2 Meso Compounds

Meso compounds are achiral compounds that has multiple chiral centers. It is superimposed on its mirror image and is optically inactive despite its stereocenters.

Introduction

In general, a meso compound should contain two or more identical substituted stereocenters. Also, it has an internal symmetry plane that divides the compound in half. These two halves reflect each other by the internal mirror. The stereochemistry of stereocenters should "cancel out". What it means here is that when we have an internal plane that splits the compound into two symmetrical sides, the stereochemistry of both left and right side should be opposite to each other, and therefore, result in optically inactive. Cyclic compounds may also be meso.

Identification

If A is a meso compound, it should have two or more stereocenters, an internal plane, and the stereochemistry should be R and S.

1. Look for an internal plane, or internal mirror, that lies in between the compound.
2. The stereochemistry (e.g. R or S) is very crucial in determining whether it is a meso compound or not. As mentioned above, a meso compound is optically inactive, so their stereochemistry should cancel out. For instance, R cancels S out in a meso compound with two stereocenters.

trans-1,2-dichloro-1,2-ethanediol

(meso)-2,3-dibromobutane

Tips: An interesting thing about single bonds or sp³-orbitals is that we can rotate the substituted groups that attached to a stereocenter around to recognize the internal plane. As the molecule is rotated, its stereochemistry does not change. For example:

Another case is when we rotate the whole molecule by 180 degree. Both molecules below are still meso.

Remember the internal plane here is depicted on two dimensions. However, in reality, it is three dimensions, so be aware of it when we identify the internal mirror.

Example

This molecule has a plane of symmetry (the horizontal plane going through the red broken line) and, therefore, is achiral; However, it has two chiral carbons and is consequentially a meso compound.

Example 2

This molecules has a plane of symmetry (the vertical plane going through the red broken line perpendicular to the plane of the ring) and, therefore, is achiral, but has has two chiral centers. Thus, its is a meso compound.

Other Examples of meso compounds

Meso compounds can exist in many different forms such as pentane, butane, heptane, and even cyclobutane. They do not necessarily have to be two stereocenters, but can have more.

Optical Activity Analysis

When the optical activity of a meso compound is attempted to be determined with a polarimeter, the indicator will not show (+) or (-). It simply means there is no certain direction of rotation of the polarized light, neither levorotatory (-) and dexorotatory (+).

Problems

Beside meso, there are also other types of molecules: enantiomer, diastereomer, and identical. Determine if the following molecules are meso.

Answer key: A C, D, E are meso compounds.

References

1. Vollhardt, K. P.C. & Shore, N. (2007). Organic Chemistry (5^thEd.). New York: W. H. Freeman. (190-192)
2. Shore, N. (2007). Study Guide and Solutions Manual for Organic Chemistry (5th Ed.). New York: W.H. Freeman. (70-80)

Contributors

• Duy Dang

• Gamini Gunawardena from the OChemPal site (Utah Valley University)

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