Tartaric acid, stereoisomers

Table sugar, sec Sucrose Tagatose, structure of, 975 Talose. configuration of, 982 Tamiflu, molecular model of, 130 Tamoxifen, synthesis of, 744 Till] DNA polymerase, PCR and, 1117 Tartaric acid, stereoisomers of, 305-306... 

Because of the plane of symmetry, the tartaric acid stereoisomer shown in Figure 9.11 must be achiral, despite the fact that it has two chirality j centers. Compounds that are achiral, yet contain chirality centers, are called meso compounds (me-zo). Thus, tartaric acid exists in tliree stereoiso-meric forms two enantiomers and one meso form. 

The grape is the only cultivated fruit of European origin that accumulates significant quantities of tartaric add. Specifically, the L-(-l-) tartaric acid stereoisomer accumulates in the grape, attaining 150 mM in the must at veraison and from 25 to 75 mM in the must at maturity (3.8-... 

The separation of a racemic mixture into its enantiomeric components is termed resolution The first resolution that of tartaric acid was carried out by Louis Pasteur m 1848 Tartaric acid IS a byproduct of wine making and is almost always found as its dextrorotatory 2R 3R stereoisomer shown here m a perspective drawing and m a Fischer projection... 

Multiple Chiral Centers. The number of stereoisomers increases rapidly with an increase in the number of chiral centers in a molecule. A molecule possessing two chiral atoms should have four optical isomers, that is, four structures consisting of two pairs of enantiomers. However, if a compound has two chiral centers but both centers have the same four substituents attached, the total number of isomers is three rather than four. One isomer of such a compound is not chiral because it is identical with its mirror image it has an internal mirror plane. This is an example of a diaster-eomer. The achiral structure is denoted as a meso compound. Diastereomers have different physical and chemical properties from the optically active enantiomers. Recognition of a plane of symmetry is usually the easiest way to detect a meso compound. The stereoisomers of tartaric acid are examples of compounds with multiple chiral centers (see Fig. 1.14), and one of its isomers is a meso compound. 

Since chirality is a property of a molecule as a whole, the specific juxtaposition of two or more stereogenic centers in a molecule may result in an achiral molecule. For example, there are three stereoisomers of tartaric acid (2,3-dihydroxybutanedioic acid). Two of these are chiral and optically active but the third is not. 

Let s look at one more example of a compound with more than one chirality center, the tartaric acid used by Pasteur. The four stereoisomers can be drawn as follows ... 

Some physical properties of the three stereoisomers are listed in Table 9.3. The (+)- and (-j-tartaric acids have identical melting points, solubilities, and densities but differ in the sign of their rotation of plane-polarized light. The meso isomer, by contrast, is diastereomeric with the (+) and (-) forms. As such, it has no mirror-image relationship to (+)- and (-)-tartaric acids, is a different compound altogether, and has different physical properties. 

Table 9,3 Some Properties of the Stereoisomers of Tartaric Acid...

In general, the maximum number of optically active isomers is given by 2n where n represents the number of asymmetric carbon atoms. Thus for a compound where n = 1, as in lactic acid, there would be two stereoisomers, one the dextro and the other the laevo. For a compound with two asymmetric carbon atoms, there would be 22 = 4 stereoisomers. But if the two asymmetric carbon atoms carry exactly identical groups, as in tartaric acid, the number would be fewer than four and we know that it exists in three forms, the d the 1 and the meso. 

Now for a rather unexpected twist. We have seen that if there are n chiral centres there should be 2" configurational isomers, and we have considered each of these for n = 2 (e.g. ephedrine, pseudoephedrine). It transpires that if the groups around chiral centres are the same, then the number of stereoisomers is less than 2". Thus, when n = 2, there are only three stereoisomers, not four. As one of the simplest examples, let us consider in detail tartaric acid, a component of grape juice and many other fruits. This fits the requirement, since each of the two chiral centres has the same substituents. 

This is essentially the same as the tartaric acid example, without the conformational complication. Thus, there are two chiral centres, and the groups around each centre are the same. Again, we get only three stereoisomers rather than four, since the cis compound is an optically inactive meso compound. There is a plane of symmetry in this molecule, and it is easy to see that one chiral centre is mirrored by the other, so that we lose optical activity. 

Let us apply these principles to tartaric acid. This compound has two chiral centres but, as we saw previously, only three stereoisomers exist, since there... 

We can draw these three stereoisomers as Fischer projections, reversing the configurations at both centres to get the enantiomeric stereoisomers, whilst the Fischer projection for the third isomer, the meso compound, is characterized immediately by a plane of symmetry. For (-l-)-tartaric acid, the configuration is 2R, >R), and for (—)-tartaric acid it is (2S,3S). For both chiral centres, the group of lowest priority is hydrogen, which is on a horizontal line. In fact, this is the case in almost all Fischer projections, since, by convention, the vertical... 

Now, let us consider another similar molecule, tartaric acid, where there are two chiral carbons. In tartaric acid, four isomeric forms are theoretically expected (2 = 4). However, because one half of the tartaric acid molecule is a mirror image of the other half, we get a meso structure. This means this compound and its mirror image are superimposable, i.e. they are the same compound. Thus, instead of four, we obtain only three stereoisomers for tartaric acid. 

RGURE 1 Pasteur separated crystals of two stereoisomers of tartaric acid and showed that solutions of the separated forms rotated polarized light to the same extent but in opposite directions. These dextrorotatory and levorotatory forms were later shown to be the (R,R) and (S,S) isomers represented here. The RS system of nomenclature is explained in the text. 

All of the threonine stereoisomers 19-22 are chiral substances that is, they are not identical with their mirror images. However, it is important to recognize that not all diastereomers are chiral. To illustrate this point, we return to the tartaric acids mentioned previously in connection with Pasteur s discoveries (Section 5-1C). 

As has been mentioned before in this chapter, tartaric acid has several stereoisomers (Figure 2). This is one reason for the complexity of its coordination chemistry, although in certain situations... 

The tartaric acids incorporate two equivalently substituted stereogenic centers. (+)-Tartaric acid, as noted in the text, is the 2R,3R stereoisomer. There will be two additional stereoisomers, the enantiomeric ( )-tartaric acid (2S,3S) and an optically inactive meso form. 

Thus if we let these three models represent different isomers of tartaric acid, we find that there are three stereoisomers for tartaric acid—a meso form and a pair of enantiomers. 

A meso form with any one of the enantiomers of tartaric acid represents a pair of diastereomers. Although it may not be true for this compound because of the meso form, in general, if you have n stereocenters, there are 2n stereoisomers possible (see Post-Lab question no. 3). 

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