The answer is that Pasteur started with a $50: 50$ mixture of the two chiral tartaric acid enantiomers. Such a mixture is called a racemate (rass-uh-mate), or racemic mixture, and is denoted by either the symbol $( \pm)$ or the prefix $d, l$ to indicate an equal mixture of dextrorotatory and levorotatory forms. Racemates show no optical rotation because the (+) rotation from one enantiomer exactly cancels the ( - ) rotation from the other. Through good luck, Pasteur was able to separate, or resolve, racemic tartaric acid into its (+) and (-) enantiomers. Unfortunately, the fractional crystallization technique he used doesn't work for most racemates, so other methods are needed.


Solution - 5.8 Racemic Mixtures and the Resolution of Enantiomers

The most common method for resolving the racemate of a chiral carboxylic acid $\left(\mathrm{RCO}_{2} \mathrm{H}\right)$ is to carry out an acidbase reaction between the acid and an amine base $\left(\mathrm{RNH}_{2}\right)$ to yield an ammonium salt:
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0145.jpg?height=220&width=700&top_left_y=1424&top_left_x=710)


To understand how this method of resolution works, let's see what happens when a racemic mixture of chiral acids, such as (+)- and (-)-lactic acids, reacts with an achiral amine base, such as methylamine, $\mathrm{CH}_{3} \mathrm{NH}_{2}$. The situation is analogous to what happens when left and right hands (chiral) pick up a ball (achiral). Both left and right hands pick up the ball equally well, and the products-ball in right hand versus ball in left hand-are mirror images. In the same way, both (+)- and (-)-lactic acid react with methylamine equally well, and the product is a racemic mixture of the two enantiomers methylammonium (+)-lactate and methylammonium (-)-lactate (FIGURE 5.13).
(R)
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(S)


Racemic lactic acid
(50\% R, 50\% S)

Racemic ammonium salt
(50\% R, 50\% S)


FIGURE 5.13 Reaction of racemic lactic acid with achiral methylamine gives a racemic mixture of ammonium salts.
Now let's see what happens when the racemic mixture of (+)- and (-)-lactic acids reacts with a single enantiomer of a chiral amine base, such as ( $R$ )-1-phenylethylamine. The situation is analogous to what happens when left and right hands (chiral) put on a right-handed glove (also chiral). Left and right hands don't put on the righthanded glove in the same way, so the products-right hand in right glove versus left hand in right glove-are not mirror images; they're similar but different.

In the same way, (+)- and (-)-lactic acids react with ( $R$ )-1-phenylethylamine to give two different products (FIGURE 5.14). ( $R$ )-Lactic acid reacts with ( $R$ )-1-phenylethylamine to give the $R, R$ salt, and ( $S$ )-lactic acid reacts with the $R$ amine to give the $S, R$ salt. The two salts are diastereomers, not enantiomers. They have different chemical and physical properties, and it may therefore be possible to separate them by crystallization or some other means. Once separated, acidification of the two diastereomeric salts with a strong acid makes it possible to isolate the two pure enantiomers of lactic acid and to recover the chiral amine for reuse.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0146.jpg?height=687&width=1383&top_left_y=1516&top_left_x=374)

FIGURE 5.14 Reaction of racemic lactic acid with ( $R$ )-1-phenylethylamine yields a mixture of diastereomeric ammonium salts, which have different properties and can be separated.


WORKED EXAMPLE 5.6 -


Predicting the Chirality of a Reaction Product -

We'll see in Section 21.3 that carboxylic acids $\left(\mathrm{RCO}_{2} \mathrm{H}\right)$ react with alcohols ( $\mathrm{R}^{\prime} \mathrm{OH}$ ) to form esters ( $\mathrm{RCO}_{2} \mathrm{R}^{\prime}$ ).


Suppose that ( $\pm$ )-lactic acid reacts with $\mathrm{CH}_{3} \mathrm{OH}$ to form the ester, methyl lactate. What stereochemistry would you expect the product(s) to have? What is the relationship of the products?
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0147.jpg?height=164&width=881&top_left_y=300&top_left_x=622)


Solution -

Reaction of a racemic acid with an achiral alcohol such as methanol yields a racemic mixture of mirror-image (enantiomeric) products.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0147.jpg?height=253&width=1107&top_left_y=622&top_left_x=509)


Solution -

PROBLEM Suppose that acetic acid $\left(\mathrm{CH}_{3} \mathrm{CO}_{2} \mathrm{H}\right)$ reacts with (S)-2-butanol to form an ester (see Worked Example 5-19 5.6). What stereochemistry would you expect the product(s) to have? What is the relationship of the products?
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0147.jpg?height=169&width=1018&top_left_y=1065&top_left_x=418)


Solution -

PROBLEM What stereoisomers would result from reaction of ( $\pm$ )-lactic acid with ( $S$ )-1-phenylethylamine, and 5-20 what is the relationship between them?


Solution - 5.9 A Review of Isomerism

As noted on several previous occasions, isomers are compounds with the same chemical formula but different structures. We've seen several kinds of isomers in the past few chapters, and it's a good idea at this point to see how they relate to one another (FIGURE 5.15).
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0147.jpg?height=525&width=1370&top_left_y=1586&top_left_x=372)


Solution - 5.9 A Review of Isomerism

FIGURE 5.15 A summary of the different kinds of isomers.
There are two fundamental types of isomers, both of which we've now encountered: constitutional isomers and stereoisomers.


Solution - 5.9 A Review of Isomerism

Constitutional isomers (Section 3.2) are compounds whose atoms are connected differently. Among the kinds of constitutional isomers we've seen are skeletal, functional, and positional isomers.


Solution - 5.9 A Review of Isomerism

| Different carbon skeletons | <smiles>CC(C)C</smiles> | and | $\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{CH}_{3}$ |
| :---: | :---: | :---: | :---: |
|  | 2-Methylpropane |  | Butane |
| Different functional groups | $\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{OH}$ | and | $\mathrm{CH}_{3} \mathrm{OCH}_{3}$ |
|  | Ethyl alcohol |  | Dimethyl ether |
| Different position of functional groups | <smiles>CC(C)N</smiles> | and | $\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{NH}_{2}$ |
|  | Isopropylamine |  | Propylamine |


Solution - 5.9 A Review of Isomerism

Stereoisomers (Section 4.2) are compounds whose atoms are connected in the same order but with a different spatial arrangement. Among the kinds of stereoisomers we've seen are enantiomers, diastereomers, and cis-trans isomers of cycloalkanes. Actually, cis-trans isomers are just a subclass of diastereomers because they are non-mirror-image stereoisomers:


Solution - 5.9 A Review of Isomerism

```
Enantiomers (nonsuperimposable mirror-image stereoisomers)
```

```
Diastereomers
(nonsuperimposable
non-mirror-image
stereoisomers)
```


Solution - 5.9 A Review of Isomerism

Configurational diastereomers


Solution - 5.9 A Review of Isomerism


Solution - 5.9 A Review of Isomerism

PROBLEM What kinds of isomers are the following pairs?
5-21 (a) (S)-5-Chloro-2-hexene and chlorocyclohexane
(b) $(2 R, 3 R)$-Dibromopentane and $(2 S, 3 R)$-dibromopentane


Solution - 5.10 Chirality at Nitrogen, Phosphorus, and Sulfur

As noted previously, the most common cause of chirality in a molecule is the presence of four different substituents bonded to a tetrahedral atom. Although that atom is usually carbon, it doesn't necessarily have to be. Nitrogen, phosphorus, and sulfur atoms are all commonly encountered in organic molecules, and can all be chirality centers. We know, for instance, that trivalent nitrogen is tetrahedral, with its lone pair of electrons acting as the fourth "substituent" (Section 1.10). Is trivalent nitrogen chiral? Does a compound such as ethylmethylamine exist as a pair of enantiomers?


The answer is both yes and no. Yes in principle, but no in practice. It turns out that most trivalent nitrogen compounds undergo a rapid umbrella-like inversion that interconverts enantiomers, so we can't isolate individual enantiomers except in special cases.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0149.jpg?height=366&width=690&top_left_y=191&top_left_x=715)


A similar situation occurs in trivalent phosphorus compounds, called phosphines, but the inversion at phosphorus is substantially slower than inversion at nitrogen, so stable chiral phosphines can be isolated. ( $R$ )and ( $S$ )-methylpropylphenylphosphine, for instance, are configurationally stable for several hours at $100{ }^{\circ} \mathrm{C}$. We'll see the importance of phosphine chirality in Section 26.7 in connection with the synthesis of chiral amino acids.
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(R)-Methylpropylphenylphosphine (configurationally stable)


Divalent sulfur compounds are achiral, but trivalent sulfur compounds called sulfonium salts $\left(\mathrm{R}_{3} \mathrm{~S}^{+}\right)$can be chiral. Like phosphines, sulfonium salts undergo relatively slow inversion, so chiral sulfonium salts are configurationally stable and can be isolated. Perhaps the best known example is the coenzyme $S$-adenosylmethionine, the so-called biological methyl donor, which is involved in many metabolic pathways as a source of $\mathrm{CH}_{3}$ groups. (The " $S$ " in the name $S$-adenosylmethionine stands for sulfur and means that the adenosyl group is attached to the sulfur atom of the amino acid methionine.) The molecule has $S$ stereochemistry at sulfur and is configurationally stable for several days at room temperature. Its $R$ enantiomer is also known but is not biologically active.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0149.jpg?height=388&width=578&top_left_y=1492&top_left_x=589)
(S)-S-Adenosylmethionine


Adenosine


Solution - 5.11 Prochirality

Closely related to the concept of chirality, and particularly important in biological chemistry, is the notion of prochirality. A molecule is said to be prochiral if it can be converted from achiral to chiral in a single chemical step. For instance, an unsymmetrical ketone like 2-butanone is prochiral because it can be converted to the chiral alcohol 2-butanol by the addition of hydrogen, as we'll see in Section 17.4.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0149.jpg?height=232&width=622&top_left_y=2188&top_left_x=749)


Solution - 5.11 Prochirality

Which enantiomer of 2-butanol is produced depends on which face of the planar carbonyl group undergoes reaction. To distinguish between the possibilities, we use the stereochemical descriptors Re and Si. Rank the
three groups attached to the trigonal, $s p^{2}$-hybridized carbon, and imagine curved arrows from the highest to second-highest to third-highest ranked substituents. The face on which the arrows curve clockwise is designated the Re face (similar to $R$ ), and the face on which the arrows curve counterclockwise is designated the $\boldsymbol{S i}$ face (similar to $S$ ). In this example, addition of hydrogen from the Re face gives ( $S$ )-2-butane, and addition from the Si face gives ( $R$ )-2-butane.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0150.jpg?height=405&width=1091&top_left_y=432&top_left_x=517)


Solution - 5.11 Prochirality

In addition to compounds with planar, $s p^{2}$-hybridized atoms, compounds with tetrahedral, $s p^{3}$-hybridized atoms can also be prochiral. An $s p^{3}$-hybridized atom is said to be a prochirality center if, by changing one of its attached groups, it becomes a chirality center. The $-\mathrm{CH}_{2} \mathrm{OH}$ carbon atom of ethanol, for instance, is a prochirality center because changing one of its attached -H atoms converts it into a chirality center.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0150.jpg?height=199&width=652&top_left_y=1039&top_left_x=734)


Solution - 5.11 Prochirality

Ethanol
To distinguish between the two identical atoms (or groups of atoms) on a prochirality center, we imagine a change that will raise the ranking of one atom over the other without affecting its rank with respect to other attached groups. On the $-\mathrm{CH}_{2} \mathrm{OH}$ carbon of ethanol, for instance, we might imagine replacing one of the ${ }^{1} \mathrm{H}$ atoms (protium) by ${ }^{2} \mathrm{H}$ (deuterium). The newly introduced ${ }^{2} \mathrm{H}$ atom ranks higher than the remaining ${ }^{1} \mathrm{H}$ atom, but it remains lower than other groups attached to the carbon. Of the two identical atoms in the original compound, the atom whose replacement leads to an $R$ chirality center is said to be pro- $\boldsymbol{R}$ and the atom whose replacement leads to an $S$ chirality center is pro-S.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0150.jpg?height=231&width=868&top_left_y=1630&top_left_x=626)


Solution - 5.11 Prochirality

A large number of biological reactions involve prochiral compounds. One of the steps in the citric acid cycle by which food is metabolized, for instance, is the addition of $\mathrm{H}_{2} \mathrm{O}$ to fumarate to give malate. Addition of -OH occurs on the Si face of a fumarate carbon and gives $(S)$-malate as product.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0150.jpg?height=272&width=706&top_left_y=2016&top_left_x=707)


Solution - 5.11 Prochirality

As another example, studies with deuterium-labeled substrates have shown that the reaction of ethanol with the coenzyme nicotinamide adenine dinucleotide $\left(\mathrm{NAD}^{+}\right)$, catalyzed by yeast alcohol dehydrogenase, occurs with exclusive removal of the pro- $R$ hydrogen from ethanol and with addition only to the Re face of $\mathrm{NAD}^{+}$.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0151.jpg?height=291&width=1172&top_left_y=191&top_left_x=474)


Solution - 5.11 Prochirality

Ethanol
NAD ${ }^{+}$
Acetaldehyde
NADH
Determining the stereochemistry of reactions at prochirality centers is a powerful method for studying detailed mechanisms in biochemical reactions. As just one example, the conversion of citrate to cis-aconitate in the citric acid cycle has been shown to occur with loss of a pro- $R$ hydrogen, implying that the OH and H groups leave from opposite sides of the molecule.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0151.jpg?height=319&width=1237&top_left_y=735&top_left_x=455)


Solution - 5.11 Prochirality

PROBLEM Identify the indicated hydrogens in the following molecules as pro- $R$ or pro- $S$ :


Solution - 5.11 Prochirality


Solution - 5.11 Prochirality

Phenylalanine


Solution - 5.11 Prochirality

PROBLEM Identify the indicated faces of carbon atoms in the following molecules as Re or Si :


Solution - 5.11 Prochirality

Crotyl alcohol


Solution - 5.11 Prochirality

PROBLEM The lactic acid that builds up in tired muscles is formed from pyruvate. If the reaction occurs with
5-24 addition of hydrogen to the Re face of pyruvate, what is the stereochemistry of the product?
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0151.jpg?height=194&width=520&top_left_y=1860&top_left_x=415)


Solution - 5.11 Prochirality

PROBLEM The aconitase-catalyzed addition of water to cis-aconitate in the citric acid cycle occurs with the
5-25 following stereochemistry. Does the addition of the OH group occur on the Re or Si face of the substrate? What about the addition of the H? Do the H and OH groups add from the same side of the double bond or from opposite sides?
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0151.jpg?height=191&width=852&top_left_y=2276&top_left_x=420)
cis-Aconitate
(2R,3S)-Isocitrate


Solution - 5.12 Chirality in Nature and Chiral Environments

Although the different enantiomers of a chiral molecule have the same physical properties, they usually have different biological properties. For example, a change in chirality can affect the biological properties of many drugs, such as fluoxetine, a heavily prescribed medication sold under the trade name Prozac. Racemic fluoxetine is an effective antidepressant but has no activity against migraine. The pure $S$ enantiomer, however, works remarkably well in preventing migraine. Other examples of how chirality affects biological properties are given in the Chapter 5 Chemistry Matters at the end of this chapter.
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(S)-Fluoxetine (prevents migraine)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0152.jpg?height=573&width=581&top_left_y=554&top_left_x=1051)


Why do different enantiomers have different biological properties? To have a biological effect, a substance typically must fit into an appropriate receptor that has a complementary shape. But because biological receptors are chiral, only one enantiomer of a chiral substrate can fit, just as only a right hand can fit into a right-handed glove. The mirror-image enantiomer will be a misfit, like a left hand in a right-handed glove. A representation of the interaction between a chiral molecule and a chiral biological receptor is shown in FIGURE 5.16: one enantiomer fits the receptor perfectly, but the other does not.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0152.jpg?height=708&width=1234&top_left_y=1413&top_left_x=443)


FIGURE 5.16 Interaction of a chiral object with a chiral receptor. A left hand interacts with a chiral object, much as a biological receptor interacts with a chiral molecule. (a) One enantiomer fits into the hand perfectly: green thumb, red palm, and gray pinkie finger, with the blue substituent exposed. (b) The other enantiomer, however, can't fit into the hand. When the green thumb and gray pinkie finger interact appropriately, the palm holds a blue substituent rather than a red one, with the red substituent exposed.


The hand-in-glove fit of a chiral substrate into a chiral receptor is relatively straightforward, but it's less obvious how a prochiral substrate can undergo a selective reaction. Take the reaction of ethanol with $\mathrm{NAD}^{+}$catalyzed by yeast alcohol dehydrogenase. As we saw at the end of Section 5.11, this reaction occurs with exclusive removal of the pro- $R$ hydrogen from ethanol and with addition only to the Re face of the $\mathrm{NAD}^{+}$carbon.


We can understand this result by imagining that the chiral enzyme receptor again has three binding sites, as in


FIGURE 5.16. When green and gray substituents of a prochiral substrate are held appropriately, however, only one of the two red substituents-say, the pro- $S$ one-is also held while the other, pro- $R$, substituent is exposed for reaction.


We describe the situation by saying that the receptor provides a chiral environment for the substrate. In the absence of a chiral environment, the two red substituents are chemically identical, but in the presence of a chiral environment, they are chemically distinctive (FIGURE 5.17a). The situation is similar to what happens when you pick up a coffee mug. By itself, the mug has a plane of symmetry and is achiral. When you pick up the mug, however, your hand provides a chiral environment so that one side becomes much more accessible and easier to drink from than the other (FIGURE 5.17b).
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0153.jpg?height=795&width=1378&top_left_y=643&top_left_x=384)

FIGURE 5.17 (a) When a prochiral molecule is held in a chiral environment, the two seemingly identical substituents are distinguishable. (b) Similarly, when an achiral coffee mug is held in the chiral environment of your hand, it's much easier to drink from one side than the other because the two sides of the mug are now distinguishable.


(0\% CHEMISTRY MATTERS -


Chiral Drugs -

The many hundreds of different pharmaceutical agents approved for use by the U.S. Food and Drug Administration come from many sources. Many drugs are isolated directly from plants or bacteria, and others are made by chemical modification of naturally occurring compounds. An estimated $33 \%$, however, are made entirely in the laboratory and have no relatives in nature.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0154.jpg?height=538&width=828&top_left_y=631&top_left_x=646)


Chiral Drugs -

FIGURE 5.18 The $S$ enantiomer of ibuprofen soothes the aches and pains of athletic injuries much more effectively than the $R$ enantiomer. (credit: "World Athletic Championships 2007 in Osaka" by Eckhard Pecher/Wikimedia Commons, CC BY 2.5)