FIGURE 23.7 MECHANISM -

2 The nucleophile adds to the $\alpha, \beta$-unsaturated ketone electrophile in a Michael reaction to generate a new enolate as product.
(3) The enolate product abstracts an acidic proton, either from solvent or from starting keto ester, to yield the final addition product.
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(1) $\| \mathrm{Na}^{+}{ }^{+}$-OEt
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(3) $\downarrow \mathrm{EtOH}$
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0829.jpg?height=183&width=535&top_left_y=1475&top_left_x=1115)


FIGURE 23.7 MECHANISM -

The Michael reaction occurs with a variety of $\alpha, \beta$-unsaturated carbonyl compounds, not just conjugated ketones. Unsaturated aldehydes, esters, thioesters, nitriles, amides, and nitro compounds can all act as the electrophilic acceptor component in Michael reactions (TABLE 23.1). Similarly, a variety of different donors can be used, including $\beta$-diketones, $\beta$-keto esters, malonic esters, $\beta$-keto nitriles, and nitro compounds.


FIGURE 23.7 MECHANISM -

TABLE 23.1 Some Michael Acceptors and Michael Donors
Michael acceptors Michael donors


FIGURE 23.7 MECHANISM -

| <smiles>C=[C]C=O</smiles> | Propenal | <smiles>O=[14C]C=[18O]</smiles> | $\beta$-Diketone |
| :---: | :---: | :---: | :---: |
| <smiles>C=CC(C)=O</smiles> | 3-Buten-2-one | <smiles>CCOC(=O)CC=O</smiles> | $\beta$-Keto ester |
| <smiles>C=C[C-]O[O-]</smiles> | Ethyl propenoate | <smiles></smiles> | Diethyl malonate |


FIGURE 23.7 MECHANISM -

TABLE 23.1 Some Michael Acceptors and Michael Donors


FIGURE 23.7 MECHANISM -

| Michael accep |  | Michael donors |  |
| :---: | :---: | :---: | :---: |
| <smiles>C=C(N)O</smiles> | Propenamide | $\stackrel{\mathrm{O}}{\mathrm{RCCH}}{ }_{2} \mathrm{C} \equiv \mathrm{~N}$ | $\beta$-Keto nitrile |
| $\mathrm{H}_{2} \mathrm{C}=\mathrm{CHC} \equiv \mathrm{N}$ | Propenenitrile | $\mathrm{RCH}_{2} \mathrm{NO}_{2}$ | Nitro compound |
| <smiles>C=CN+[O-]</smiles> | Nitroethylene |  |  |


WORKED EXAMPLE 23.5 -


Using the Michael Reaction -


Strategy -

A Michael reaction involves the conjugate addition of a stable enolate ion donor to an $\alpha, \beta$-unsaturated carbonyl acceptor, yielding a 1,5-dicarbonyl product. Usually, the stable enolate ion is derived from a $\beta$-diketone, $\beta$-keto ester, malonic ester, or similar compound. The $C-C$ bond formed in the conjugate addition step is the one between the $\alpha$ carbon of the acidic donor and the $\beta$ carbon of the unsaturated acceptor.


Solution -


Solution -

PROBLEM What product would you obtain from a base-catalyzed Michael reaction of 2,4-pentanedione with 23-16 each of the following $\alpha, \beta$-unsaturated acceptors?
(a) 2-Cyclohexenone
(b) Propenenitrile
(c) Ethyl 2-butenoate


Solution -

PROBLEM How would you prepare the following compound using a Michael reaction (gray = H, black = C, red 23-18 = O, blue = N)?
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0831.jpg?height=302&width=617&top_left_y=185&top_left_x=407)


Solution - 23.11 Carbonyl Condensations with Enamines: The Stork Enamine Reaction

In addition to enolate ions, other kinds of carbon nucleophiles also add to $\alpha, \beta$-unsaturated acceptors in Michaellike reactions. Among the most important and useful of such nucleophiles, particularly in biological chemistry, are enamines, which are readily prepared by reaction between a ketone and a secondary amine (Section 19.8). For example:
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0831.jpg?height=291&width=915&top_left_y=760&top_left_x=605)


As the following resonance structures indicate, enamines are electronically similar to enolate ions. Overlap of the nitrogen lone-pair orbital with the double-bond $p$ orbitals leads to an increase in electron density on the $\alpha$ carbon atom, making that carbon nucleophilic. An electrostatic potential map of $N, N$-dimethylaminoethylene shows this shift of electron density (red) toward the $\alpha$ position.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0831.jpg?height=659&width=1328&top_left_y=1286&top_left_x=387)


Enamines behave in much the same way as enolate ions and enter into many of the same kinds of reactions. In the Stork enamine reaction, named for its discoverer, Gilbert Stork of Columbia University, for example, an enamine adds to an $\alpha, \beta$-unsaturated carbonyl acceptor in a Michael-like process. The initial product is then hydrolyzed by aqueous acid to yield a 1,5 -dicarbonyl compound. The overall reaction is thus a threestep sequence of (1) enamine formation from a ketone, (2) Michael addition to an $\alpha, \beta$-unsaturated carbonyl compound, and (3) enamine hydrolysis back to a ketone.

The net effect of the Stork enamine reaction is the Michael addition of a ketone to an $\alpha, \beta$-unsaturated carbonyl compound. For example, cyclohexanone reacts with the cyclic amine pyrrolidine to yield an enamine; further reaction with an enone such as 3-buten-2-one yields a Michael adduct; and aqueous hydrolysis completes the sequence to give a 1,5-diketone (FIGURE 23.8).
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0832.jpg?height=698&width=1527&top_left_y=177&top_left_x=299)

FIGURE 23.8 The Stork enamine reaction between cyclohexanone and 3-buten-2-one. (1) Cyclohexanone is first converted into an enamine, (2) the enamine adds to the $\alpha, \beta$-unsaturated ketone in a Michael reaction, and (3) the conjugate addition product is hydrolyzed to yield a 1,5-diketone.


The enamine-Michael reaction has two advantages over the enolate-ion-Michael reaction that makes it particularly useful in biological pathways. First, an enamine is neutral, easily prepared, and easily handled, while an enolate ion is charged, sometimes difficult to prepare, and must be handled carefully. Second, an enamine from a monoketone can be used in the Michael addition, whereas only enolate ions from $\beta$-dicarbonyl compounds can be used.


WORKED EXAMPLE 23.6 -


Using the Stork Enamine Reaction -


Strategy -

The overall result of an enamine reaction is the Michael addition of a ketone as donor to an $\alpha, \beta$-unsaturated carbonyl compound as acceptor, yielding a 1,5-dicarbonyl product. The $\mathrm{C}-\mathrm{C}$ bond formed in the Michael addition step is the one between the $\alpha$ carbon of the ketone donor and the $\beta$ carbon of the unsaturated acceptor.


Strategy -

Solution
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0832.jpg?height=348&width=1430&top_left_y=1910&top_left_x=342)


Strategy -

PROBLEM What products would result after hydrolysis from reaction of the enamine prepared from
23-19 cyclopentanone and pyrrolidine with the following $\alpha, \beta$-unsaturated acceptors?
(a) $\mathrm{H}_{2} \mathrm{C}=\mathrm{CHCO}_{2} \mathrm{Et}$
(b) $\mathrm{H}_{2} \mathrm{C}=\mathrm{CHCHO}$
(c) $\mathrm{CH}_{3} \mathrm{CH}=\mathrm{CHCOCH}_{3}$


Strategy -


Strategy - 23.12 The Robinson Annulation Reaction

Carbonyl condensation reactions are perhaps the most versatile methods available for synthesizing complex molecules. By putting a few fundamental reactions together in the proper sequence, some remarkably useful transformations can be carried out. One such example is the Robinson annulation reaction for the synthesis of polycyclic molecules. The word annulation derives from the Latin annulus, meaning "ring," so an annulation reaction is one that builds a new ring onto a molecule.


Named after Robert Robinson, a British chemist and 1947 Nobel Prize winner, the Robinson annulation is a two-step process that combines a Michael reaction with an intramolecular aldol reaction. It takes place between a nucleophilic donor, such as a $\beta$-keto ester; an enamine, or a $\beta$-diketone; and an $\alpha, \beta$-unsaturated ketone acceptor, such as 3-buten-2-one. The product is a substituted 2 -cyclohexenone.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0833.jpg?height=267&width=1563&top_left_y=926&top_left_x=281)

The first step of the Robinson annulation is simply a Michael reaction. An enamine or an enolate ion from a $\beta$-keto ester or $\beta$-diketone effects a conjugate addition to an $\alpha, \beta$-unsaturated ketone, yielding a 1,5 -diketone. But as we saw in Section 23.6, 1,5-diketones undergo intramolecular aldol condensation to yield cyclohexenones when treated with base. Thus, the final product contains a six-membered ring, and an annulation has been accomplished. One example of this occurs during a synthesis of the steroid hormone estrone (FIGURE 23.9).
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0833.jpg?height=787&width=1432&top_left_y=1425&top_left_x=349)

FIGURE 23.9 Synthesis of the steroid hormone estrone using a Robinson annulation reaction. The nucleophilic donor is a $\beta$-diketone.
In this example, the $\beta$-diketone 2 -methyl-1,3-cyclopentanedione is used to generate the enolate ion required for Michael reaction and an aryl-substituted $\alpha, \beta$-unsaturated ketone is used as the acceptor. Base-catalyzed Michael reaction between the two partners yields an intermediate triketone, which then cyclizes in an intramolecular aldol condensation to give a Robinson annulation product. Several further transformations are required to complete the synthesis of estrone.


PROBLEM What product would you expect from a Robinson annulation reaction of
23-21 2-methyl-1,3-cyclopentanedione with 3-buten-2-one?
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0834.jpg?height=226&width=682&top_left_y=299&top_left_x=445)


2-Methyl-1,3-cyclo- 3-Buten-2-one pentanedione -

PROBLEM How would you prepare the following compound using a Robinson annulation reaction between
23-22 a $\beta$-diketone and an $\alpha, \beta$-unsaturated ketone? Draw the structures of both reactants and the intermediate Michael addition product.
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2-Methyl-1,3-cyclo- 3-Buten-2-one pentanedione - 23.13 Some Biological Carbonyl Condensation Reactions


Biological Aldol Reactions -

Aldol reactions occur in many biological pathways but are particularly common in carbohydrate metabolism, where enzymes called aldolases catalyze the addition of a ketone enolate ion to an aldehyde. Aldolases occur in all organisms and are of two types. Type I aldolases occur primarily in animals and higher plants; type II aldolases occur primarily in fungi and bacteria. Both types catalyze the same kind of reaction, but type I aldolases operate through an enamine while type II aldolases require a metal ion (usually $\mathrm{Zn}^{2+}$ ) as a Lewis acid and operate through an enolate ion.

An example of an aldolase-catalyzed reaction occurs in glucose biosynthesis when dihydroxyacetone phosphate reacts with glyceraldehyde 3 -phosphate to give fructose 1,6-bisphosphate. In animals and higher plants, dihydroxyacetone phosphate is first converted into an enamine by reaction with the $-\mathrm{NH}_{2}$ group on a lysine amino acid in the enzyme. The enamine then adds to glyceraldehyde 3-phosphate, and the iminium ion that results is hydrolyzed. In bacteria and fungi, the aldol reaction occurs directly, with the ketone carbonyl group of glyceraldehyde 3-phosphate complexed to a $\mathrm{Zn}^{2+}$ ion to make it a better acceptor.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0835.jpg?height=665&width=1613&top_left_y=188&top_left_x=256)


Type II aldolase -


Type II aldolase -

Glyceraldehyde 3-phosphate


Fructose -


Fructose -

Note that the aldolase-catalyzed reactions are mixed aldol reactions, which take place between two different partners, as opposed to the symmetrical aldol reactions between identical partners usually carried out in the laboratory. Mixed aldol reactions often give mixtures of products in the laboratory but are successful in living systems because of the selectivity of the enzyme catalysts.


Biological Claisen Condensations -

Claisen condensations, like aldol reactions, also occur in a large number of biological pathways. In fatty-acid biosynthesis, for instance, an enolate ion generated by decarboxylation (Section 22.7) of malonyl ACP adds to the carbonyl group of another acyl group bonded through a thioester linkage to a synthase enzyme. The tetrahedral intermediate that results then expels the synthase, giving acetoacetyl ACP. (The abbreviation ACP stands for acyl carrier protein, which forms thioester bonds to acyl groups.)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0836.jpg?height=640&width=1264&top_left_y=187&top_left_x=425)

Mixed Claisen condensations also occur frequently in living organisms, particularly in the pathway for fattyacid biosynthesis that we'll discuss in Section 29.4. Butyryl synthase, for instance, reacts with malonyl ACP in a mixed Claisen condensation to give 3-ketohexanoyl ACP.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0836.jpg?height=286&width=1408&top_left_y=974&top_left_x=364)


A Prologue to Metabolism -

Biochemistry is carbonyl chemistry. Almost all metabolic pathways used by living organisms involve one or more of the four fundamental carbonyl-group reactions we've seen in the chapters on Aldehydes and Ketones: Nucleophilic Addition Reactions through Carbonyl Condensation Reactions. The digestion and metabolic breakdown of all the major classes of food molecules-fats, carbohydrates, and proteins-take place by nucleophilic addition reactions, nucleophilic acyl substitutions, $\alpha$ substitutions, and carbonyl condensations. Similarly, hormones and other crucial biological molecules are built up from smaller precursors by these same carbonyl-group reactions.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0837.jpg?height=909&width=768&top_left_y=765&top_left_x=673)


A Prologue to Metabolism -

FIGURE 23.10 You are what you eat. Food molecules are metabolized by pathways that involve the four major carbonyl-group reactions. (credit: "Spring" by Giuseppe Arcimboldo, Louvre Museum/Wikimedia Commons, Public Domain)


A Prologue to Metabolism -

Take glycolysis, for example, the metabolic pathway by which organisms convert glucose to pyruvate as the first step in extracting energy from carbohydrates.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0837.jpg?height=286&width=825&top_left_y=1860&top_left_x=647)


A Prologue to Metabolism -

Glycolysis is a ten-step process that begins with isomerization of glucose from its cyclic hemiacetal form to its open-chain aldehyde form-the reverse of a nucleophilic addition reaction. The aldehyde then undergoes tautomerization to yield an enol, which undergoes yet another tautomerization to give the ketone fructose.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0838.jpg?height=464&width=1365&top_left_y=180&top_left_x=380)


A Prologue to Metabolism -

Fructose, a $\beta$-hydroxy ketone, is then cleaved by a retro-aldol reaction into two three-carbon molecules-one ketone and one aldehyde. Further carbonyl-group reactions then occur until pyruvate is formed.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0838.jpg?height=434&width=925&top_left_y=737&top_left_x=600)


A Prologue to Metabolism -

These few examples are only an introduction; we'll look at several of the major metabolic pathways in more detail in Chapter 29. The bottom line, however, is that you haven't seen the end of carbonyl-group chemistry if you have any interest in biological or medical fields. A solid grasp of carbonyl-group reactions is crucial to an understanding of biochemistry.


Key Terms -

- aldol reaction
- carbonyl condensation reaction
- Claisen condensation reaction
- Dieckmann cyclization
- Michael reaction
- Robinson annulation reaction
- Stork enamine reaction


Key Terms -


Summary -

In this chapter, we've discussed the fourth and last of the common carbonyl-group reactions-the carbonyl condensation. A carbonyl condensation reaction takes place between two carbonyl partners and involves both nucleophilic addition and $\alpha$-substitution processes. One carbonyl partner is converted by base into a nucleophilic enolate ion, which then adds to the electrophilic carbonyl group of the second partner. The first partner thus undergoes an $\alpha$ substitution, while the second undergoes a nucleophilic addition.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0838.jpg?height=188&width=769&top_left_y=1971&top_left_x=678)


Summary -

$$
\begin{array}{cc}
\text { Nucleophilic } & \text { Electrophilic } \\
\text { donor } & \text { acceptor }
\end{array}
$$


Summary -

The aldol reaction is a carbonyl condensation that occurs between two aldehyde or ketone molecules. Aldol reactions are reversible, leading first to $\beta$-hydroxy aldehydes/ketones and then to $\alpha, \beta$-unsaturated products after dehydration. Mixed aldol condensations between two different aldehydes or ketones generally give a mixture of all four possible products. A mixed reaction can be successful, however, if one of the two partners is an unusually good donor (ethyl acetoacetate, for instance) or if it can act only as an acceptor (formaldehyde and benzaldehyde, for instance). Intramolecular aldol condensations of 1,4- and 1,5-diketones are also successful and provide a good way to make five- and six-membered rings.


Summary -

The Claisen condensation reaction is a carbonyl condensation that occurs between two ester components and gives a $\beta$-keto ester product. Mixed Claisen condensations between two different esters are successful only when one of the two partners has no acidic $\alpha$ hydrogens (ethyl benzoate and ethyl formate, for instance) and thus can function only as the acceptor partner. Intramolecular Claisen condensations, called Dieckmann cyclization reactions, yield five- and six-membered cyclic $\beta$-keto esters starting from 1,6-and 1,7-diesters.


Summary -

The conjugate addition of a carbon nucleophile to an $\alpha, \beta$-unsaturated acceptor is known as the Michael reaction. The best Michael reactions take place between relatively acidic donors ( $\beta$-keto esters or $\beta$-diketones) and unhindered $\alpha, \beta$-unsaturated acceptors. Enamines, prepared by reaction of a ketone with a disubstituted amine, are also good Michael donors in the Stork enamine reaction.


Summary -

Carbonyl condensation reactions are widely used in synthesis. One example of their versatility is the Robinson annulation reaction, which leads to the formation of a substituted cyclohexenone. Treatment of a $\beta$-diketone or $\beta$-keto ester with an $\alpha, \beta$-unsaturated ketone leads first to a Michael addition, which is followed by intramolecular aldol cyclization. Condensation reactions are also used widely in nature for the biosynthesis of such molecules as fats and steroids.


Summary of Reactions -

1. Aldol reaction (Section 23.1)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0839.jpg?height=147&width=613&top_left_y=981&top_left_x=783)
2. Mixed aldol reaction (Section 23.5)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0839.jpg?height=161&width=760&top_left_y=1166&top_left_x=710)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0839.jpg?height=161&width=765&top_left_y=1351&top_left_x=710)
3. Intramolecular aldol reaction (Section 23.6)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0839.jpg?height=199&width=987&top_left_y=1554&top_left_x=599)
4. Dehydration of aldol products (Section 23.3)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0839.jpg?height=174&width=760&top_left_y=1794&top_left_x=712)
5. Claisen condensation reaction (Section 23.7)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0839.jpg?height=156&width=893&top_left_y=2009&top_left_x=643)
6. Mixed Claisen condensation reaction (Section 23.8)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0839.jpg?height=156&width=1015&top_left_y=2204&top_left_x=585)
7. Intramolecular Claisen condensation (Dieckmann cyclization; Section 23.9)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0840.jpg?height=177&width=942&top_left_y=188&top_left_x=624)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0840.jpg?height=199&width=936&top_left_y=394&top_left_x=627)
8. Michael reaction (Section 23.10)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0840.jpg?height=210&width=1009&top_left_y=627&top_left_x=588)
9. Carbonyl condensations with enamines (Stork enamine reaction; Section 23.11)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0840.jpg?height=169&width=1128&top_left_y=880&top_left_x=523)


Additional Problems -

Visualizing Chemistry
PROBLEM What ketones or aldehydes might the following enones have been prepared from by aldol reaction?
23-23 (a)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0840.jpg?height=383&width=556&top_left_y=1261&top_left_x=481)
(b)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0840.jpg?height=372&width=483&top_left_y=1272&top_left_x=1122)


Additional Problems -

PROBLEM The following structure represents an intermediate formed by addition of an ester enolate ion to a
23-24 second ester molecule. Identify the reactant, the leaving group, and the product.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0840.jpg?height=432&width=730&top_left_y=1790&top_left_x=410)


Additional Problems -


Additional Problems -

PROBLEM The following molecule was formed by a Robinson annulation reaction. What reactants were used? 23-26
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0841.jpg?height=370&width=481&top_left_y=582&top_left_x=421)


Mechanism Problems -

PROBLEM Predict the addition product for each of the following reactions and write the mechanism.


Mechanism Problems -


Mechanism Problems -

PROBLEM Based on your answers to Problem 23-27, predict the dehydration product for both reactions and 23-28 write the mechanism.


Mechanism Problems -

PROBLEM Predict the product(s) and provide the mechanisms for the following reactions.
23-29 (a)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0841.jpg?height=171&width=950&top_left_y=1465&top_left_x=479)
(b)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0841.jpg?height=147&width=576&top_left_y=1661&top_left_x=482)

PROBLEM Predict the product(s) and provide the mechanisms for the following reactions.
23-30 (a)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0841.jpg?height=131&width=985&top_left_y=1902&top_left_x=481)
(b)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0841.jpg?height=137&width=1025&top_left_y=2051&top_left_x=485)

PROBLEM Predict the product(s) and provide the mechanisms for the following reactions.
23-31 (a)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0841.jpg?height=126&width=736&top_left_y=2271&top_left_x=483)
(b)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0842.jpg?height=193&width=833&top_left_y=218&top_left_x=478)


Mechanism Problems -

PROBLEM Knoevenagel condensation is a reaction involving an active methylene compound (a $\mathrm{CH}_{2}$ flanked
23-32 by two electron-withdrawing groups) and an aldehyde and ketone. Propose a mechanism for the reaction below.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0842.jpg?height=277&width=1402&top_left_y=585&top_left_x=416)


Mechanism Problems -

PROBLEM Azlactones are important starting materials used in the synthesis of dehydro $\alpha$-aminoacids. They
23-33 react with aldehydes to form an intermediate that is hydrolyzed under acidic conditions to give the final amino acid product. Provide the structure of the intermediate and propose a mechanism for its formation.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0842.jpg?height=278&width=1368&top_left_y=1078&top_left_x=411)


Azlactone -

Deydro- $\alpha$-amino acid
PROBLEM Leucine, one of the twenty amino acids found in proteins, is metabolized by a pathway that includes 23-34 the following step. Propose a mechanism.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0842.jpg?height=280&width=1064&top_left_y=1543&top_left_x=414)

PROBLEM Isoleucine, another of the twenty amino acids found in proteins, is metabolized by a pathway that 23-35 includes the following step. Propose a mechanism.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0842.jpg?height=278&width=1042&top_left_y=1948&top_left_x=414)


Azlactone -

PROBLEM The first step in the citric acid cycle of food metabolism is reaction of oxaloacetate with acetyl CoA 23-36 to give citrate. Propose a mechanism, using acid or base catalysis as needed.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0842.jpg?height=186&width=1050&top_left_y=2349&top_left_x=413)


Azlactone -

PROBLEM The amino acid leucine is biosynthesized from $\alpha$-ketoisovalerate by the following sequence of steps.
23-37 Show the mechanism of each.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0843.jpg?height=487&width=1445&top_left_y=304&top_left_x=416)


Azlactone -

PROBLEM The Knoevenagel reaction was introduced in Problem 23-2. Show the mechanism for the 23-38 Knoevenagel reaction of diethyl malonate with benzaldehyde.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0843.jpg?height=208&width=1270&top_left_y=915&top_left_x=411)


Azlactone -

Benzaldehyde
Cinnamic acid (91\%)
PROBLEM The Darzens reaction involves a two-step, base-catalyzed condensation of ethyl chloroacetate with
23-39 a ketone to yield an epoxy ester. The first step is a carbonyl condensation reaction, and the second step is an $\mathrm{S}_{\mathrm{N}} 2$ reaction. Write both steps, and show their mechanisms.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0843.jpg?height=153&width=915&top_left_y=1349&top_left_x=410)


Azlactone -

PROBLEM The following reaction involves a hydrolysis followed by an intramolecular nucleophilic acyl 23-40 substitution reaction. Write both steps, and show their mechanisms.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0843.jpg?height=237&width=863&top_left_y=1616&top_left_x=411)

PROBLEM The following reaction involves an intramolecular Michael reaction followed by an intramolecular 23-41 aldol reaction. Write both steps, and show their mechanisms.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0843.jpg?height=226&width=1017&top_left_y=1979&top_left_x=413)

PROBLEM The following reaction involves a conjugate addition reaction followed by an intramolecular Claisen
23-42 condensation. Write both steps, and show their mechanisms.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0844.jpg?height=239&width=841&top_left_y=187&top_left_x=414)

PROBLEM The following reaction involves an intramolecular aldol reaction followed by a retro aldol-like 23-43 reaction. Write both steps, and show their mechanisms.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0844.jpg?height=267&width=774&top_left_y=555&top_left_x=418)


Azlactone -

PROBLEM Propose a mechanism for the following base-catalyzed isomerization:
23-44
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0844.jpg?height=259&width=814&top_left_y=906&top_left_x=414)


Azlactone -

PROBLEM The Mannich reaction of a ketone, an amine, and an aldehyde is one of the few three-component
23-45 reactions in organic chemistry. Cyclohexanone, for example, reacts with dimethylamine and acetaldehyde to yield an amino ketone. The reaction takes place in two steps, both of which are typical carbonyl-group reactions.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0844.jpg?height=210&width=1128&top_left_y=1380&top_left_x=409)
(a) The first step is reaction between the aldehyde and the amine to yield an intermediate iminium ion $\left(\mathrm{R}_{2} \mathrm{C}=\mathrm{NR}_{2}{ }^{+}\right)$plus water. Propose a mechanism, and show the structure of the intermediate iminium ion.
(b) The second step is reaction between the iminium ion intermediate and the ketone to yield the final product. Propose a mechanism.


Azlactone -

PROBLEM Cocaine has been prepared by a sequence beginning with a Mannich reaction (Problem 23-45)
23-46 between dimethyl acetonedicarboxylate, an amine, and a dialdehyde. Show the structures of the amine and dialdehyde.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0844.jpg?height=337&width=1278&top_left_y=1984&top_left_x=410)


Azlactone -

PROBLEM Propose a mechanism to account for the following reaction of an enamine with an alkyl halide: 23-47
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0845.jpg?height=291&width=969&top_left_y=191&top_left_x=410)


Aldol Reactions -

PROBLEM Which of the following compounds would you expect to undergo aldol self-condensation? Show the 23-48 product of each successful reaction.
(a) Trimethylacetaldehyde
(b) Cyclobutanone
(c) Benzophenone (diphenyl ketone)
(d) 3-Pentanone
(e) Decanal
(f) 3-Phenyl-2-propenal