General Problems -

PROBLEM In glycerol metabolism, the oxidation of sn-glycerol 3-phosphate to give dihydroxyacetone
29-51 phosphate is catalyzed by sn-glycerol-3-phosphate dehydrogenase, with NAD ${ }^{+}$as cofactor. The reaction is stereospecific, occurring exclusively on the Re face of the nicotinamide ring.
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$N A D^{+}$
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General Problems -

NADH


General Problems -

Which hydrogen in the NADH product comes from sn-glycerol 3-phosphate? Does it have pro- $R$ or pro- $S$ stereochemistry?


General Problems -

PROBLEM The primary fate of acetyl CoA under normal metabolic conditions is degradation in the citric 29-52 acid cycle to yield $\mathrm{CO}_{2}$. When the body is stressed by prolonged starvation, however, acetyl CoA is converted into compounds called ketone bodies, which can be used by the brain as a temporary fuel. Fill in the missing information indicated by the four question marks in the following biochemical pathway for the synthesis of ketone bodies from acetyl CoA:
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General Problems -


General Problems -

Ketone bodies
PROBLEM The initial reaction in Problem 29-52, conversion of two molecules of acetyl CoA to one molecule of 29-53 acetoacetyl CoA, is a Claisen reaction. Assuming that there is a base present, show the mechanism
of the reaction.
PROBLEM In step 6 of fatty-acid biosynthesis (Figure 29.6), acetoacetyl ACP is reduced stereospecifically by 29-54 NADPH to yield an alcohol. Does hydride ion add to the Si face or the Re face of acetoacetyl ACP?
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General Problems -

Acetoacetyl ACP
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1088.jpg?height=172&width=565&top_left_y=369&top_left_x=753)
$\beta$-Hydroxybutyryl ACP


General Problems -

PROBLEM In step 7 of fatty-acid biosynthesis (Figure 29.6), dehydration of a $\beta$-hydroxy thioester occurs to give 29-55 trans-crotonyl ACP. Is the dehydration a syn elimination or an anti elimination?
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1088.jpg?height=245&width=779&top_left_y=734&top_left_x=413)

PROBLEM In step 8 of fatty-acid biosynthesis (Figure 29.6), reduction of trans-crotonyl ACP gives butyryl ACP.
29-56 A hydride from NADPH adds to C3 of the crotonyl group from the Re face, and protonation on C2 occurs on the Si face. Is the reduction a syn addition or an anti addition?
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1088.jpg?height=194&width=660&top_left_y=1150&top_left_x=418)


CHAPTER 30 -

Orbitals and Organic Chemistry: Pericyclic Reactions
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1089.jpg?height=754&width=1888&top_left_y=596&top_left_x=235)


CHAPTER 30 -

FIGURE 30.1 It may look easy, but these sunbathers are working hard to carry out a pericyclic reaction. (credit: modification of work "Tanning" by Meraj Chhaya/Flickr, CC BY 2.0).


CHAPTER CONTENTS -

30.1 Molecular Orbitals of Conjugated Pi Systems
30.2 Electrocyclic Reactions
30.3 Stereochemistry of Thermal Electrocyclic Reactions
30.4 Photochemical Electrocyclic Reactions
30.5 Cycloaddition Reactions
30.6 Stereochemistry of Cycloadditions
30.7 Sigmatropic Rearrangements
30.8 Some Examples of Sigmatropic Rearrangements
30.9 A Summary of Rules for Pericyclic Reactions


CHAPTER CONTENTS -

WHY THIS CHAPTER? Broad outlines of both polar and radical reactions have been in place for more than a century, but our understanding of pericyclic reactions has emerged more recently. Prior to the mid-1960s, in fact, they were even occasionally referred to as "no-mechanism reactions." They occur largely in the laboratory rather than in biological processes, but a knowledge of them is necessary, both for completeness in studying organic chemistry and in understanding biological pathways where they do occur.


CHAPTER CONTENTS -

Most organic reactions take place by polar mechanisms, in which a nucleophile donates two electrons to an electrophile in forming a new bond. Other reactions take place by radical mechanisms, in which each of two reactants donates one electron in forming a new bond. Both kinds of reactions occur frequently in the laboratory and in living organisms. Less common, however, is the third major class of organic reactions-pericyclic reactions.


CHAPTER CONTENTS -

A pericyclic reaction is one that occurs by a concerted process through a cyclic transition state. A concerted reaction is one in which all bonding changes occur simultaneously; no intermediates are involved. Rather than try to expand this definition now, we'll begin by briefly reviewing some of the ideas of molecular orbital theory introduced in the chapters on Structure and Bonding and Conjugated Compounds and Ultraviolet Spectroscopy and then looking individually at the three main classes of pericyclic reactions: electrocyclic reactions, cycloadditions, and sigmatropic rearrangements.


CHAPTER CONTENTS - 30.1 Molecular Orbitals of Conjugated Pi Systems

A conjugated polyene, as we saw in Section 14.1, is one with alternating double and single bonds. According to molecular orbital (MO) theory, the $p$ orbitals on the $s p^{2}$-hybridized carbons of a conjugated polyene interact to form a set of $\pi$ molecular orbitals whose energies depend on the number of nodes they have between nuclei. Molecular orbitals with fewer nodes are lower in energy than isolated $p$ atomic orbitals and are bonding MOs; molecular orbitals with more nodes are higher in energy than isolated $p$ orbitals and are antibonding MOs. Pi molecular orbitals of ethylene and 1,3-butadiene are shown in FIGURE 30.2.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1090.jpg?height=996&width=1640&top_left_y=819&top_left_x=237)


A similar sort of molecular orbital description can be derived for any conjugated $\pi$ electron system. 1,3,5-Hexatriene, for example, has three double bonds and six $\pi$ MOs, as shown in FIGURE 30.3. In the ground state, only the three bonding orbitals, $\psi_{1}, \psi_{2}$, and $\psi_{3}$, are filled. On irradiation with ultraviolet light, however, an electron is promoted from the highest-energy filled orbital $\left(\psi_{3}\right)$ to the lowest-energy unfilled orbital ( $\psi_{4} *$ ) to give an excited state (Section 14.7), in which $\psi_{3}$ and $\psi_{4}{ }^{*}$ are each half-filled. (An asterisk denotes an antibonding orbital.)


What do molecular orbitals and their nodes have to do with pericyclic reactions? The answer is, everything. According to a series of rules formulated in the mid-1960s by R. B. Woodward and Roald Hoffmann at Harvard University, a pericyclic reaction can take place only if the symmetries of the reactant MOs are the same as the symmetries of the product MOs. In other words, the lobes of reactant MOs must be of the correct algebraic sign for bonding to occur in the transition state leading to product.


If the symmetries of reactant and product orbitals match up, or correlate, the reaction is said to be symmetryallowed. If the symmetries of reactant and product orbitals don't correlate, the reaction is symmetrydisallowed. Symmetry-allowed reactions often occur under relatively mild conditions, but symmetrydisallowed reactions can't occur by concerted paths. They either take place by nonconcerted, higher-energy
pathways, or they don't take place at all.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1091.jpg?height=1098&width=1677&top_left_y=275&top_left_x=243)


Ground state Excited state
FIGURE 30.3 The six $\boldsymbol{\pi}$ molecular orbitals of 1,3,5-hexatriene. In the ground state, the three bonding MOs, $\psi_{1}, \psi_{2}$, and $\psi_{3}$, are filled. In the excited state, $\psi_{3}$ and $\psi_{4}{ }^{*}$ are both half-filled.


The Woodward-Hoffmann rules for pericyclic reactions require an analysis of all reactant and product molecular orbitals, but Kenichi Fukui at Kyoto Imperial University in Japan introduced a simplified version. Hoffman and Fukui shared a Nobel Prize for their work, and Woodward would have joined them (for his second Nobel Prize) had he not passed away before the award was made. According to Fukui's simplified version, we need to consider only two molecular orbitals, called the frontier orbitals. These frontier orbitals are the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). In ground-state $1,3,5$-hexatriene, for example, $\psi_{3}$ is the HOMO and $\psi_{4}{ }^{*}$ is the LUMO (FIGURE 30.3). In excitedstate 1,3,5-hexatriene, however, $\psi_{4}{ }^{*}$ is the HOMO and $\psi_{5}{ }^{*}$ is the LUMO.


PROBLEM Look at Figure 30.2, and tell which molecular orbital is the HOMO and which is the LUMO for both 30-1 ground and excited states of ethylene and 1,3-butadiene.


CHAPTER CONTENTS - 30.2 Electrocyclic Reactions

The best way to understand how orbital symmetry affects pericyclic reactions is to look at some examples. Let's look first at a group of polyene rearrangements called electrocyclic reactions. An electrocyclic reaction is a pericyclic process that involves the cyclization of a conjugated acyclic polyene. One $\pi$ bond is broken, the other $\pi$ bonds change position, a new $\sigma$ bond is formed, and a cyclic compound results. For example, a conjugated triene can be converted into a cyclohexadiene, and a conjugated diene can be converted into a cyclobutene.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1092.jpg?height=134&width=470&top_left_y=188&top_left_x=833)


A conjugated triene -

A cyclohexadiene
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1092.jpg?height=134&width=418&top_left_y=448&top_left_x=859)


A conjugated diene -


A cyclobutene -

Pericyclic reactions are reversible, and the position of the equilibrium depends on the specific case. In general, the triene $\rightleftarrows$ cyclohexadiene equilibrium favors the cyclic product, whereas the diene $\rightleftarrows$ cyclobutene equilibrium favors the less strained open-chain product.


A cyclobutene -

The most striking feature of electrocyclic reactions is their stereochemistry. For example, ( $2 E, 4 Z, 6 E$ )-2,4,6-octatriene yields only cis-5,6-dimethyl-1,3-cyclohexadiene when heated, and ( $2 E, 4 Z, 6 Z$ )-2,4,6-octatriene yields only trans- 5,6 -dimethyl-1,3-cyclohexadiene. Remarkably, however, the stereochemical results change completely when the reactions are carried out under what are called photochemical, rather than thermal, conditions. Irradiation of ( $2 E, 4 Z, 6 E$ )-2,4,6-octatriene with ultraviolet light (denoted hv) yields trans-5,6-dimethyl-1,3-cyclohexadiene (FIGURE 30.4).
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1092.jpg?height=261&width=589&top_left_y=1081&top_left_x=714)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1092.jpg?height=424&width=641&top_left_y=1344&top_left_x=712)
$\begin{array}{cc}(2 E, 4 Z, 6 Z)-2,4,6- & \text { trans-5,6-Dimethyl-1,3- } \\ \text { Octatriene } & \text { cyclohexadiene }\end{array}$
FIGURE 30.4 Electrocyclic interconversions of 2,4,6-octatriene isomers and 5,6-dimethyl-1,3-cyclohexadiene isomers.
A similar result is obtained for the thermal electrocyclic ring-opening of 3,4-dimethylcyclobutene. The trans isomer yields only $(2 E, 4 E)-2,4$-hexadiene when heated, and the cis isomer yields only ( $2 E, 4 Z$ )-2,4-hexadiene. On UV irradiation, however, the results are opposite. Cyclization of the $2 E, 4 E$ isomer under photochemical conditions yields cis product (FIGURE 30.5).
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1093.jpg?height=801&width=1345&top_left_y=193&top_left_x=387)


A cyclobutene -

To account for these results, we need to look at the two outermost lobes of the polyene MOs-the lobes that interact when cyclization occurs. There are two possibilities: lobes of like sign can be either on the same side of the molecule or on opposite sides.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1093.jpg?height=245&width=318&top_left_y=1192&top_left_x=611)


A cyclobutene -

Like lobes on same side
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1093.jpg?height=242&width=321&top_left_y=1191&top_left_x=1195)

Like lobes on opposite side


A cyclobutene -

For a bond to form, the outermost $\pi$ lobes must rotate so that favorable bonding interaction is achieved-a positive lobe with a positive lobe or a negative lobe with a negative lobe. If two lobes of like sign are on the same side of the molecule, the two orbitals must rotate in opposite directions-one clockwise and one counterclockwise. This kind of motion is referred to as disrotatory.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1093.jpg?height=315&width=985&top_left_y=1713&top_left_x=554)

Conversely, if lobes of like sign are on opposite sides of the molecule, both orbitals must rotate in the same direction, either both clockwise or both counterclockwise. This kind of motion is called conrotatory.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1093.jpg?height=321&width=980&top_left_y=2149&top_left_x=556)


A cyclobutene - 30.3 Stereochemistry of Thermal Electrocyclic Reactions

How can we predict whether conrotatory or disrotatory motion will occur in a given case? According to frontier orbital theory, the stereochemistry of an electrocyclic reaction is determined by the symmetry of the polyene HOMO. The electrons in the HOMO are the highest-energy, most loosely held electrons and are therefore most easily moved during reaction. For thermal reactions, the ground-state electron configuration is used to identify the HOMO; for photochemical reactions, the excited-state electron configuration is used.


Let's look again at the thermal ring-closure of conjugated trienes. According to FIGURE 30.3, the HOMO of a conjugated triene in its ground state has lobes of like sign on the same side of the molecule, a symmetry that predicts disrotatory ring-closure. This disrotatory cyclization is precisely what is observed in the thermal cyclization of $2,4,6$-octatriene. The $2 E, 4 Z, 6 E$ isomer yields cis product; the $2 E, 4 Z, 6 Z$ isomer yields trans product (FIGURE 30.6).
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1094.jpg?height=771&width=1221&top_left_y=772&top_left_x=468)

In the same way, the ground-state HOMO of conjugated dienes (FIGURE 30.2) has a symmetry that predicts conrotatory ring-closure. In practice, however, the conjugated diene reaction can be observed only in the reverse direction (cyclobutene $\rightarrow$ diene) because of the position of the equilibrium. We therefore find that the 3,4-dimethylcyclobutene ring opens in a conrotatory fashion. cis-3,4-Dimethylcyclobutene yields ( $2 E, 4 Z$ )-2,4-hexadiene, and trans-3,4-dimethylcyclobutene yields ( $2 E, 4 E$ )-2,4-hexadiene by conrotatory opening (FIGURE 30.7).
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1094.jpg?height=614&width=1131&top_left_y=1856&top_left_x=475)


FIGURE 30.7 Thermal ring-openings of cis- and trans-dimethylcyclobutene occur by conrotatory paths.


Note that a conjugated diene and a conjugated triene react with opposite stereochemistry. The diene opens and closes by a conrotatory path, whereas the triene opens and closes by a disrotatory path. This is due to the different symmetries of the diene and triene HOMOs.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1095.jpg?height=237&width=288&top_left_y=348&top_left_x=645)


Diene номо
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1095.jpg?height=235&width=413&top_left_y=346&top_left_x=1043)


Triene HOMO


It turns out that there is an alternating relationship between the number of electron pairs (double bonds) undergoing bond reorganization and the stereochemistry of ring-opening or -closure. Polyenes with an even number of electron pairs undergo thermal electrocyclic reactions in a conrotatory sense, whereas polyenes with an odd number of electron pairs undergo the same reactions in a disrotatory sense.


PROBLEM Draw the products you would expect from conrotatory and disrotatory cyclizations of 30-2 ( $2 Z, 4 Z, 6 Z$ )-2,4,6-octatriene. Which of the two paths would you expect the thermal reaction to follow?


PROBLEM trans-3,4-Dimethylcyclobutene can open by two conrotatory paths to give either 30-3 ( $2 E, 4 E$ )-2,4-hexadiene or ( $2 Z, 4 Z$ )-2,4-hexadiene. Explain why both products are symmetryallowed, and then account for the fact that only the $2 E, 4 E$ isomer is obtained in practice.


A cyclobutene - 30.4 Photochemical Electrocyclic Reactions

We noted previously that photochemical electrocyclic reactions take a different stereochemical course than their thermal counterparts, and we can now explain this difference. Ultraviolet irradiation of a polyene causes an excitation of one electron from the ground-state HOMO to the ground-state LUMO, thus changing their symmetries. But because electronic excitation changes the symmetries of HOMO and LUMO, it also changes the reaction stereochemistry. ( $2 E, 4 E$ )-2,4-Hexadiene, for instance, undergoes photochemical cyclization by a disrotatory path, whereas the thermal reaction is conrotatory. Similarly, ( $2 E, 4 Z, 6 E$ )-2,4,6-octatriene undergoes photochemical cyclization by a conrotatory path, whereas the thermal reaction is disrotatory (FIGURE 30.8).
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1095.jpg?height=950&width=1702&top_left_y=1536&top_left_x=236)


FIGURE 30.8 Photochemical cyclizations of conjugated dienes and trienes. The two processes occur with different stereochemistry because of their different orbital symmetries.


Thermal and photochemical electrocyclic reactions always take place with opposite stereochemistry because the symmetries of the frontier orbitals are always different. TABLE 30.1 gives some simple rules that make it possible to predict the stereochemistry of electrocyclic reactions.


| TABLE 30.1 Stereochemical Rules for Electrocyclic Reactions |  |  |  |
| :--- | :--- | :--- | :---: |
| Electron pairs (double bonds) | Thermal reaction | Photochemical reaction |  |
| Even number | Conrotatory | Disrotatory |  |
| Odd number | Disrotatory | Conrotatory |  |


PROBLEM What product would you expect to obtain from the photochemical cyclization of 30-4 (2E,4Z,6E)-2,4,6-octatriene? Of ( $2 E, 4 Z, 6 Z$ )-2,4,6-octatriene?


A cyclobutene - 30.5 Cycloaddition Reactions

A cycloaddition reaction is one in which two unsaturated molecules add to one another to yield a cyclic product. As with electrocyclic reactions, cycloadditions are governed by the orbital symmetry of the reactants. Symmetry-allowed processes often take place readily, but symmetry-disallowed processes take place with difficulty, if at all, and then only by nonconcerted pathways. Let's look at two examples to see how they differ.


As we saw in Section 14.4, the Diels-Alder cycloaddition reaction is a pericyclic process that takes place between a diene (four $\pi$ electrons) and a dienophile (two $\pi$ electrons) to yield a cyclohexene product. Many thousands of Diels-Alder reactions are known. They often take place easily at room temperature or slightly above, and they are stereospecific with respect to substituents. For example, room-temperature reaction between 1,3-butadiene and diethyl maleate (cis) exclusively yields the cis-disubstituted cyclohexene product. A similar reaction between 1,3-butadiene and diethyl fumarate (trans) exclusively yields the trans-disubstituted product.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1096.jpg?height=570&width=933&top_left_y=1374&top_left_x=593)


In contrast to the [4 +2$]$ - $\pi$-electron Diels-Alder reaction, the $[2+2]$ - $\pi$-electron cycloaddition between two alkenes does not occur thermally. The [2 + 2] cycloaddition takes place only on irradiation, yielding cyclobutane products.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1096.jpg?height=348&width=760&top_left_y=2097&top_left_x=672)


A cyclobutane


For a successful cycloaddition, the terminal $\pi$ lobes of the two reactants must have the correct symmetry for bonding to occur. This can happen in either of two ways, called suprafacial and antarafacial. Suprafacial cycloadditions take place when a bonding interaction occurs between lobes on the same face of one reactant and lobes on the same face of the other reactant. Antarafacial cycloadditions take place when a bonding interaction occurs between lobes on the same face of one reactant and lobes on opposite faces of the other reactant (FIGURE 30.9).
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1097.jpg?height=519&width=1177&top_left_y=483&top_left_x=443)
(b) Antarafacial
Like lobes
on opposite
faces
Like lobes on same face
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1097.jpg?height=497&width=886&top_left_y=1031&top_left_x=726)

FIGURE 30.9 (a) Suprafacial cycloaddition occurs when there is bonding between lobes on the same face of one reactant and lobes on the same face of the other reactant. (b) Antarafacial cycloaddition occurs when there is bonding between lobes on the same face of one reactant and lobes on opposite faces of the other, which requires a twist in one $\pi$ system.

Note that both suprafacial and antarafacial cycloadditions are symmetry-allowed. Geometric constraints often make antarafacial reactions difficult, however, because there must be a twisting of the $\pi$ orbital system in one of the reactants. Thus, suprafacial cycloadditions are much more common for small $\pi$ systems.


A cyclobutene - 30.6 Stereochemistry of Cycloadditions

How can we predict whether a given cycloaddition reaction will occur with suprafacial or with antarafacial geometry? According to frontier orbital theory, a cycloaddition reaction takes place when a bonding interaction occurs between the HOMO of one reactant and the LUMO of the other. An intuitive explanation of this rule is to imagine that one reactant donates electrons to the other. As with electrocyclic reactions, it's the electrons in the HOMO of the first reactant that are least tightly held and most likely to be donated. Of course when the second reactant accepts those electrons, they must go into a vacant, unoccupied orbital-the LUMO.

For a [4 + 2] cycloaddition (Diels-Alder reaction), let's arbitrarily select the diene LUMO and the alkene HOMO. The symmetries of the two ground-state orbitals are such that bonding of the terminal lobes can occur with suprafacial geometry (FIGURE 30.10), so the Diels-Alder reaction takes place readily under thermal conditions. Note that, as with electrocyclic reactions, we need be concerned only with the terminal lobes. For purposes of prediction, interactions among the interior lobes need not be considered.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1098.jpg?height=411&width=1202&top_left_y=220&top_left_x=426)

FIGURE 30.10 Interaction of diene LUMO and alkene HOMO in a suprafacial [4 + 2] cycloaddition reaction (Diels-Alder reaction).
In contrast with the thermal [4 + 2] Diels-Alder reaction, the [2 + 2] cycloaddition of two alkenes to yield a cyclobutane can only occur photochemically. The explanation for this follows from orbital-symmetry arguments. Looking at the ground-state HOMO of one alkene and the LUMO of the second alkene, it's apparent that a thermal $[2+2]$ cycloaddition must take place by an antarafacial pathway (FIGURE 30.11a). Geometric constraints make the antarafacial transition state difficult, however, and so concerted thermal [2 + 2] cycloadditions are not observed.
In contrast with the thermal process, photochemical [2 + 2] cycloadditions are observed. Irradiation of an alkene with UV light excites an electron from $\psi_{1}$, the ground-state HOMO, to $\psi_{2}{ }^{*}$, which becomes the excited-state HOMO. Interaction between the excited-state HOMO of one alkene and the LUMO of the second alkene allows a photochemical [2 + 2] cycloaddition reaction to occur by a suprafacial pathway (FIGURE 30.11b).
(a) Thermal reaction
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1098.jpg?height=563&width=554&top_left_y=1250&top_left_x=506)


Strained, no reaction
(b) Photochemical reaction


Alkene 2: Ground-state LUMO

Alkene 1:
Excited-state HOMO
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1098.jpg?height=308&width=217&top_left_y=1841&top_left_x=1431)


FIGURE 30.11 (a) Interaction of a ground-state HOMO and a ground-state LUMO in a potential [2 + 2] cycloaddition does not occur thermally because the antarafacial geometry is too strained. (b) Interaction of an excited-state HOMO and a ground-state LUMO in a photochemical [2+2] cycloaddition reaction is less strained, however, and occurs with suprafacial geometry.


The photochemical [2+2] cycloaddition reaction occurs smoothly, particularly with $\alpha, \beta$-unsaturated carbonyl compounds, and represents one of the best methods known for synthesizing cyclobutane rings. For example:
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1099.jpg?height=240&width=763&top_left_y=189&top_left_x=708)


2-Cyclohexenone
2-Methylpropene
(40\%)
Thermal and photochemical cycloaddition reactions always take place with opposite stereochemistry. As with electrocyclic reactions, we can categorize cycloadditions according to the total number of electron pairs (double bonds) involved in the rearrangement. Thus, a thermal [ $4+2]$ Diels-Alder reaction between a diene and a dienophile involves an odd number (three) of electron pairs and takes place by a suprafacial pathway. A thermal $[2+2]$ reaction between two alkenes involves an even number (two) of electron pairs and must take place by an antarafacial pathway. For photochemical cyclizations, these selectivities are reversed. These general rules are given in TABLE 30.2.


TABLE 30.2 Stereochemical Rules for Cycloaddition Reactions


| Electron pairs (double bonds) | Thermal reaction | Photochemical reaction |
| :--- | :--- | :--- |
| Even number | Antarafacial | Suprafacial |
| Odd number | Suprafacial | Antarafacial |


PROBLEM What stereochemistry would you expect for the product of the Diels-Alder reaction between 30-5 ( $2 E, 4 E$ )-2,4-hexadiene and ethylene? What stereochemistry would you expect if $(2 E, 4 Z)-2,4$-hexadiene were used instead?


PROBLEM 1,3-Cyclopentadiene reacts with cycloheptatrienone to give the product shown. Tell what kind of 30-6 reaction is involved, and explain the observed result. Is the reaction suprafacial or antarafacial?
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1099.jpg?height=285&width=961&top_left_y=1405&top_left_x=411)


A cyclobutene - 30.7 Sigmatropic Rearrangements

A sigmatropic rearrangement, the third general kind of pericyclic reaction, is a process in which a $\sigma$-bonded substituent atom or group migrates across a $\pi$ electron system from one position to another. A $\sigma$ bond is broken in the reactant, the $\pi$ bonds move, and a new $\sigma$ bond is formed in the product. The $\sigma$-bonded group can be either at the end or in the middle of the $\pi$ system, as the following $[1,5]$ and $[3,3]$ rearrangements illustrate:


A [1,5] sigmatropic rearrangement -


A [3,3] sigmatropic rearrangement -


A [3,3] sigmatropic rearrangement -

The notations [1,5] and [3,3] describe the kind of rearrangement that is occurring. The numbers refer to the two groups connected by the $\sigma$ bond in the reactant and designate the positions in those groups to which migration occurs. For example, in the [1,5] sigmatropic rearrangement of a 1,3-diene, the two groups connected by the $\sigma$ bond are a hydrogen atom and a pentadienyl group. Migration occurs to position 1 of the H group (the only possibility) and to position 5 of the pentadienyl group. In the [3,3] rearrangement of an allylic vinylic ether, the two groups connected by the $\sigma$ bond are an allylic group and the vinylic ether. Migration occurs to position 3 of the allylic group and also to position 3 of the vinylic ether.


A [3,3] sigmatropic rearrangement -

Like electrocyclic reactions and cycloadditions, sigmatropic rearrangements are controlled by orbital symmetries. There are two possible modes of reaction: migration of a group across the same face of the $\pi$ system is suprafacial, and migration of a group from one face of the $\pi$ system to the other face is antarafacial (FIGURE 30.12).
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1101.jpg?height=849&width=887&top_left_y=191&top_left_x=611)

FIGURE 30.12 Suprafacial and antarafacial sigmatropic rearrangements.
Both suprafacial and antarafacial sigmatropic rearrangements are symmetry-allowed, but suprafacial rearrangements are often easier for geometric reasons. The rules for sigmatropic rearrangements are identical to those for cycloaddition reactions (TABLE 30.3).


A [3,3] sigmatropic rearrangement -

TABLE 30.3 Stereochemical Rules for Sigmatropic Rearrangements


A [3,3] sigmatropic rearrangement -

PROBLEM Classify the following sigmatropic reaction by order $[x, y]$, and tell whether it will proceed with 30-7 suprafacial or antarafacial stereochemistry:
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1101.jpg?height=175&width=459&top_left_y=1750&top_left_x=410)


A [3,3] sigmatropic rearrangement - 30.8 Some Examples of Sigmatropic Rearrangements

Because a $[1,5]$ sigmatropic rearrangement involves three electron pairs (two $\pi$ bonds and one $\sigma$ bond), the orbital-symmetry rules in TABLE 30.3 predict a suprafacial reaction. In fact, the [1,5] suprafacial shift of a hydrogen atom across two double bonds of a $\pi$ system is a commonly observed sigmatropic rearrangements. For example, 5-methyl-1,3-cyclopentadiene rapidly rearranges at room temperature to yield a mixture of 1-methyl-, 2-methyl-, and 5-methyl-isomers.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1101.jpg?height=231&width=863&top_left_y=2248&top_left_x=634)


As another example, heating 5,5,5-trideuterio-(3Z)-1,3-pentadiene causes scrambling of deuterium between
positions 1 and 5.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1102.jpg?height=161&width=617&top_left_y=256&top_left_x=754)


Both these $[1,5]$ hydrogen shifts occur by a symmetry-allowed suprafacial pathway, as illustrated in FIGURE 30.13. In contrast with these thermal [1,5] sigmatropic hydrogen shifts, however, thermal [1,3] hydrogen shifts are unknown. If they were to occur, they would have to proceed by a strained antarafacial reaction pathway.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1102.jpg?height=345&width=1177&top_left_y=630&top_left_x=466)


FIGURE 30.13 An orbital view of a suprafacial [1,5] hydrogen shift.
Two other important sigmatropic reactions are the Claisen rearrangement of either an allyl aryl ether $\left(\mathrm{H}_{2} \mathrm{C}=\mathrm{CHCH}_{2}-\mathrm{O}-\mathrm{Ar}\right)$ or an allyl vinyl $\left(\mathrm{H}_{2} \mathrm{C}=\mathrm{CHCH}_{2}-\mathrm{O}-\mathrm{CH}=\mathrm{CH}_{2}\right)$ ether, and the Cope rearrangement of a 1,5 hexadiene to an isomeric 1,5-diene. These two rearrangements, along with the Diels-Alder reaction, are among the most generally useful pericyclic reactions for organic synthesis. Thousands of examples of all three are known.


Claisen rearrangement -


Claisen rearrangement -

An allylic
vinylic ether


Claisen rearrangement -

An unsaturated ketone


Claisen rearrangement -

Cope rearrangement
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1102.jpg?height=250&width=557&top_left_y=2106&top_left_x=681)


Claisen rearrangement -

Like the Diels-Alder reaction discussed in Section 14.4 and Section 14.5, the Claisen rearrangement takes place in a single step through a pericyclic mechanism in which a reorganization of bonding electrons occurs in a six-membered, cyclic transition state. The 6-allyl-2,4-cyclohexadienone intermediate then isomerizes to o-allylphenol (FIGURE 30.14).
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1103.jpg?height=400&width=1391&top_left_y=185&top_left_x=378)


Claisen rearrangement -

Evidence for this mechanism comes from the observation that the rearrangement takes place with transposition of the allyl group. That is, allyl phenyl ether containing a ${ }^{14} \mathrm{C}$ label on the allyl ether carbon atom yields $o$-allylphenol in which the label is on the terminal vinylic carbon (green in FIGURE 30.14).


Claisen rearrangement -

PROBLEM Draw a curved-arrow mechanism for the Cope arrangement just shown.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1103.jpg?height=169&width=1020&top_left_y=799&top_left_x=325)


Claisen rearrangement -

The Cope rearrangement that converts a 1,5-diene to an isomeric 1,5-diene is somewhat limited but a modification called the Oxy Cope Rearrangement is wider in scope. As shown in the following example, a 1-5 diene with an -OH next to the double bond can be converted into an oxy-anion by reaction with a strong base such as potassium hydride (KH). A Cope rearrangement then occurs, and reaction with aqueous acid gives an enol that tautomerizes to an aldehyde.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1103.jpg?height=150&width=919&top_left_y=1215&top_left_x=603)


Claisen rearrangement -

Although biological examples of pericyclic reactions are relatively rare, a much-studied example occurs in bacteria during biosynthesis of the essential amino acid phenylalanine. Phenylalanine arises from the precursor chorismate through a Claisen rearrangement to prephenate, followed by decarboxylation to phenylpyruvate and reductive amination (FIGURE 30.16). You might note that the reductive amination of phenylpyruvate is the exact reverse of the transamination process shown in FIGURE 29.17, by which amino acids are deaminated. In addition, the reductive amination of ketones is a standard method for preparing amines in the laboratory, as we saw in Section 24.6.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1104.jpg?height=882&width=1331&top_left_y=226&top_left_x=397)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1104.jpg?height=418&width=1470&top_left_y=1141&top_left_x=325)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1104.jpg?height=104&width=269&top_left_y=1585&top_left_x=337)
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Claisen rearrangement -

Phenylalanine
FIGURE 30.16 Pathway for the bacterial biosynthesis of phenylalanine from chorismate, involving a Claisen rearrangement.
PROBLEM Propose a mechanism to account for the fact that heating 1-deuterioindene scrambles the isotope 30-9 label to all three positions on the five-membered ring.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1104.jpg?height=245&width=1069&top_left_y=1973&top_left_x=406)


Claisen rearrangement -

1-Deuterioindene
PROBLEM What product would you expect from Claisen rearrangement of 2-butenyl phenyl ether? 30-10
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1105.jpg?height=153&width=568&top_left_y=181&top_left_x=407)


Claisen rearrangement -

2-Butenyl phenyl ether
PROBLEM When a 2,6-disubstituted allyl phenyl ether is heated in an attempted Claisen rearrangement,
30-11 migration occurs to give the $p$-allyl product as the result of two sequential pericyclic reactions. Explain.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-1105.jpg?height=325&width=878&top_left_y=564&top_left_x=412)


Claisen rearrangement - 30.9 A Summary of Rules for Pericyclic Reactions

How can you keep straight all the rules about pericyclic reactions? The summary in TABLE 30.1, TABLE 30.2, and TABLE 30.3 can be distilled into a mnemonic phrase that provides an easy way to predict the stereochemical outcome of any pericyclic reaction: