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13 Pericyclic Reactions

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13.1 What is meant by ‘pericyclic reaction’? Give classifi- Ene reactions:

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cations of pericyclic reactions with examples. H H
W Z W Z

at
Ans Woodward and Hoffmann have suggested the term peri- +
cyclic reactions (the word means around the circle) for those X Y X Y

M
reactions which are (a) concerted, that is, reactant-bonds are
broken and product-bonds are formed simultaneously by way Note that a π-bond is converted into σ-bond,
of a single transition state and (b) involve electrons shift in a
cyclic manner. Pericyclic reactions have no intermediates but
ed but no rings are formed or broken
ht
they have cyclic conjugated transition states. The four prin- 13.2 What is meant by FMO theory in pericyclic reac-
tions? Give an example.
ig

ciple classes of pericyclic reactions are termed cycloaddition,


electrocyclic, sigmatropic, and ene reactions. A general illus- Ans Valance shell electrons of atoms take part in the bond
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tration of each class is given here. The corresponding intra- formation in chemical reaction. According to molecular
op

molecular reactions, which create an additional ring, are also orbital theory, two atomic orbitals generate two molecular
well known. orbitals, one with lower energy and the other with higher
energy compared to the energy state of the participating
-C

Cycloaddition reactions:
atomic orbitals. If each atomic orbital contains one electron
A new ring is formed then two electrons of the two atomic orbitals move to the low-
est-energy molecular orbital and a covalent bond is formed.
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C C C– C The other molecular orbital having higher energy, remains


ie

[m + n]
+
unoccupied. In such a case, the occupied molecular orbital is
ev

called HOMO (highest occupied molecular orbital) and the


C C C– C unoccupied molecular is called LUMO (lowest unoccupied
mπ-electrons nπ-electrons (m + n − 4) π-electrons
Pr

molecular orbital). HOMO has electron donor property and


Note that two π-bonds are converted into two σ-bonds LUMO has electron acceptor property. Fukui in 1971 showed
that in case of concerted cycloaddition pericyclic reactions,
Electrocyclic reactions:
C
the reaction can occur if HOMO and LUMO of two inter-
C
acting species give bonding overlap. Thus, HOMO–LUMO
A new ring
is formed interaction can explain certain pericyclic reactions and have
C C been designated as ‘Frontier Molecular Orbital Theory’
m π- electrons (m−2)π- electrons (FMO theory).
Note that one π-bond is converted into one σ-bond For example, non-formation of cyclobutane from two
molecules of ethene under thermal condition can be well
Sigmatropic reactions: R explained on the basis of the FMO theory. This is shown
[1,3]-shift
C=C – C – C=C here.
R 1 2 3 4 5

C – C=C – C=C LUMO


1 2 3 4 5
R
[1,5]-shift Energy
C=C – C=C – C p-orbital p-orbital
HOMO
1 2 3 4 5
Note that the number of π-electrons has not changed π-Molecular orbitals of ethene

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352 Problems and Solutions in Organic Chemistry

When two molecules of ethylene try to combine to form 13.4 How does FMO approach of explanation of certain
cyclobutane, then HOMO of one ethylene should overlap type of pericyclic reactions helps to understand the stereo-
with LUMO of the other. However, that gives an out of phase chemical outcome of reactions? Give an example.
interaction, that is symmetry forbidden, and reaction does not Ans Stereochemical outcome of certain pericyclic reactions are
occur. This is diagrammatically shown here. well explained on the basis of FMO theory of HOMO–LUMO
concept. For example, in case of ring formation from acyclic
H2C CH2 LUMO of ethylene conjugated system and ring opening of cyclic conjugated system
Not a bonding ∆ can be well explained by FMO theory. In case of thermal reac-
Bonding overlap
overlap tion, symmetry allowed interaction involving HOMO and in
H2C CH2 HOMO of ethylene Cyclobutane case of photochemical reaction, symmetry allowed interaction
of LUMO are taken to be in consideration to explain the stereo-
However, ethylene can form cyclobutane under photo- chemical outcome of such reactions. Examples are given here.
chemical condition. Under this condition, HOMO of ground It has been found that in case of (2E,4Z,6E)-octa-2,4,6-
state is excited to HOMO of excited state and symmetry triene, thermal ring closure gives trans-5,6-dimethylcy-
allowed interaction can occur to form cyclobutane. clohexa-1,3-diene. This stereochemical outcome is well
explained on the basis of HOMO of the parent compound.

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hν This is shown in the following diagram.

er
HOMO of ethylene HOMO of ethylene Disrotatory movement of the
in ground state in excited state terminal p-orbitals

at
1 8
H3C CH3 Me Me Me Me

M
2 7
H2C CH2 HOMO of ethylene in excited state
3 6
Bonding hν H H
overlap
H2C
Bonding overlap
CH2 HOMO of ethylene Cyclobutane
ed
(2E, 4Z, 6E)-
4 5

Ψ3 cis isomer
ht
Octa-2,4,6-triene HOMO (Bonding M.O.)
ig

13.3 What are symmetry allowed and symmetry forbid- Conrotatory movement of the
den reactions? terminal p-orbitals
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Ans In case of FMO approach to a pericyclic reaction when 1 8


Me H
op

HOMO and LUMO overlap in the same phase leading to H3C 2 7


CH3 Me Me
bonding interaction then it is called symmetry allowed reac- 3 6
H Me
-C

tion but when HOMO–LUMO overlap is not a bonding inter- 4 5


action, then that is known as symmetry forbidden reaction. (2E, 4Z, 6E)- *
Ψ4 trans aisomer
Here the terms symmetry allowed and symmetry forbidden are Octa-2,4,6-triene
LUMO (Antibonding M.O.)
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different from stereochemical aspects. These are shown in the


following diagram. Photochemical cyclization
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For the three π-bonds in the parent compound, six π-molec-


ev

HOMO of ethylene ular orbitals are possible. For the thermal ring closure, HOMO
(ψ3) is to be taken into consideration and for the photochem-
Pr

ical ring closure, (ψ4*) is to be considered. On the basis of


these arguments, the stereochemical outcomes, as shown here
LUMO of ethylene
earlier, are well explained.
Symmetry forbidden interaction 13.5 How can you explain by FMO approach that buta-
(Antibonding)
1,3-diene cannot dimerize to form cycloocta-1,5-diene on
heating but forms a cyclohexene derivative by Diels–Alder
HOMO of butadiene reaction?
Ans Thermal cycloaddition between two molecules of buta-1,3-
diene to form cycloocta-2,5-diene should involve HOMO of one
LUMO of ethylene molecule and LUMO of the other. However, one of the terminals
leads to antibonding overlapping according to FMO approach.
Symmetry allowed interaction
(Bonding) This is shown here. This is why cyclooctadiene is not formed.
Heat
The dashed lines identify bonding overlap, which can develop +
as the reaction proceeds. It must be noted that symmetry forbid-
den reaction can also occur but not in a concerted manner. Buta-1,3-diene Cycloocta-2,5-diene

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Me Me
H H
(2E,4E)-isomer Pericyclic Reactions 353

(Contd) Heat
Conrotatory
ψ2 movements Me H
(HOMO) Bonding of terminal orbitals
Heat H Me
No cycloaddition Me Me
Antibonding trans-1,2-
H H
Dimethylcyclobutane
ψ3 HOMO with
(LUMO) C2-symmetry
(ψ2)
In case of Diels–Alder reaction HOMO of a diene part
reacts with LUMO of a dienophile. In this case FMO theory Photochemical ring closure of (2E, 4E)-hexa-2,4-diene:
gives symmetry allowed cycloaddition. This is shown here.
Me Me
Diene H H
(2E,4E)-isomer
ψ2
(HOMO) Bonding 4π + 2π
Cycloaddition Photochemical
Bonding

l
Disrotatory

ia
ψ3 Diels–Alder adduct
movements H H
(LUMO) of terminal orbitals

er
Me Me
Dienophile Me Me cis-1,2-
H H

at
13.6 Summarize the selection rules for electrocyclic reac- Dimethylcyclobutane
LUMO with plane
tions based on FMO theory. Give examples to show that

M
of symmetry
the outcomes of certain pericyclic reactions are corrobo- (ψ*1)
rated by these rules.
Ans The selection rules for electrocyclic reactions on the ed
Experimental results fully corroborate the products pre-
dicted on the aforementioned selection rules, regarding elec-
ht
basis of FMO theory are given here. trocyclic ring closure.
Selection rules for electrocyclic reactions
ig

13.7 Thermal ring opening of trans-3,4-dimethylcyclobut-


Number of Mode of
MO involved Allowed 1-ene and photochemical ring opening of cis-3,4-dimethyl-
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electrons activation
with the stereo cyclobutene-1-ene give the same stereochemical outcomes.
op

involved element of chemical Give reasons for these observations.


symmetry course Ans According to the selection rules for electrocyclic reac-
-C

4n Thermal HOMO with C2 Conrotatory tions, thermal ring closure and ring opening involving 4n elec-
symmetry trons occurs in a conrotatory manner. This conrotation way of
4n Photochemical LUMO with σ Disrotatory ring opening trans-3,4-dimethylcyclobut-1-ene can proceed in
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plane two different ways leading to the formation of (2E,4E)-buta-


2,4-diene and (2Z,4Z)-buta-2,4-diene. This is shown here.
ie

4n + 2 Thermal HOMO with σ Disrotatory


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plane π-bond
4n + 2 Photochemical LUMO with C2 Conrotatory Me H
Pr

(n = positive symmetry
integer)
H σ-bond Me
On the basis of the principle of microscopic reversibility, Conrotatory
it can be concluded that the selection rules for electrocyclic
ring-closure reactions apply equally well to electrocyclic Thermal
ring-opening reactions. The applicability of the rules has been
supported by many reactions. One of them is thermal and pho- Me Me
tochemical ring closure of diastereoisomeric dimethyl hexa- H H
Me Me (2E., 4E)-hexa-2,4-diene
2,3-diene. The reactions are shown here. H H
Thermal ring closure of (2E, 4E)-hexa-2,4-diene: π-bond

Me Me Me H
H H
(2E,4E)-isomer σ-bond
H Me

Heat Conrotatory

Conrotatory (Contd) Thermal (Contd)


movements Me H
of terminal orbitals
H Me H H
Me Me trans-1,2- Me Me
H H H H
Dimethylcyclobutane Me Me (2Z., 4Z)-hexa-2,4-diene
HOMO with
C2-symmetry
PSOC_Chapter 13.indd 353 (ψ2) 8/14/2014 2:53:41 PM
π-bond

Me H

354 Problems and Solutions in Organic Chemistry


H σ-bond Me
(Contd) Conrotatory
LUMO
Thermal Bonding Antibonding
HOMO
H H
Me Me
H H (2Z., 4Z)-hexa-2,4-diene
Me Me The terms suprafacial (s) and antarafacial (a) were intro-
duced by Woodward and Hoffmann to denote the stereo-
When the reaction is carried out photochemically on chemistry of a reaction with reference faces of a system of
cis-3,4-dimethylcyclobutene-1-ene, then the process of ring π-electrons or orbitals.
opening takes place by disrotatory movement of the orbitals. Suprafacial implies a process, which involves only one
This is shown here. face of the system and antarafacial, implies that both faces of
the system are involved in the reaction.
π-bond

H H Suprafacial
way of bond formation

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Me σ-bond Me

er
Disrotatory

Thermal

at
Antarafacial
way of bond formation

M
Me Me
H H
Me Me
H H (2Z., 4E)-hexa-2,4-diene
ed
ht
π-bond Cycloaddition reactions involving two different π-electron
systems can have four possible combinations.
ig

H H
yr

Me σ-bond Me
op

Disrotatory
-C

Thermal
supra–supra supra–antara

H H
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Me Me
H H (2Z., 4Z)-hexa-2,4-diene
ie

Me Me
ev

Therefore, it is found that thermal ring opening of trans-


antara–supra antara–antara
3,4-dimethylcyclobut-1-ene and photochemical ring opening
Pr

of cis-3,4-dimethylcyclobutene-1-ene give same pairs of dias- Stereochemical outcomes of the aforementioned modes of
tereoisomeric buta-1,3-diene. cycloadditions are given here.
13.8 What are meant by suprafacial and antarafacial (a) supra–supra interactions lead to retention of configura-
modes of cycloadditions? What are stereochemical out- tions at the reacting centre in question.
comes of such cycloaddition reactions. (b) The supra–antara and antara–supra modes of interaction
are indistinguishable when the two reacting systems are
Ans Cycloaddition reactions involve interaction between
identical.
π-bonds of HOMO of one component and that of LUMO of
(c) In supra–antara and antara–supra modes of interaction,
another component. Now the π-bonds are formed from dumb-
retention-inversion and inversion-retention of configura-
bell-shaped p-orbitals having two phases, usually shown by
tions occurs respectively at the reacting centres.
shaded and non-shaded lobes or by + and − signs. Bonding
(d) In antara–antara interactions, inversions of configura-
interaction in cycloaddition occurs when two similar types of
tion take place at both the reacting centres
lobes of HOMO of one component and LUMO of the other
interact, that is, two shaded lobes or two non-shaded lobes. 13.9 Show with examples that Diels–Alder reaction is a
Interaction between a shaded lobe and a non-shaded lobe supra-supra cycloaddition and the reaction leads to reten-
gives antibonding character. This is diagrammatically shown tion of stereochemistry of both diene and dienophile parts
here. in Diels–Alder reaction.

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Pericyclic Reactions 355

Ans When buta-1,3-diene and trans-1,2-dicyanoethylene 13.10 What are meant by exo- and endo products of
undergo Diels–Alder cycloaddition then stereochemistry of cycloaddition reactions? Give products in the reaction
the dienophile is retained in the product, because of supra- between cyclopentadiene and maleic anhydride with
supra interaction. This is shown by the following diagrams. explanations? Give the IUPAC names of the products.
CN
How can you distinguish them by a chemical reaction?
+ Ans One important fact regarding the stereochemistry of
the Diels–Alder reaction is that when both the diene and
NC
dienophile are substituted then the stereochemical relation-
ship of these substituents may have two possibilities. One
is called endo-addition (endo-addition rule) and the other
R S exo-addition.
CN CN
+ In endo-addition, a transition state is formed in which the
dienophile substituents are directly under (or over) the diene
R CN S CN
double bonds in a parallel planes.
(1R,2R)-Cyclohex-4-ene- (1S,2S)-Cyclohex-4-ene- In exo-addition, the dienophile is flipped relative to the
1,2-dicarbonitrile 1,2-dicarbonitrile diene and the addition occurs to the opposite face of the dieno-

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phile and this mode of addition leads to the formation of an

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Diene plane isomeric product in which substituents on the dienophile pro-
HOMO ject away from the diene.
of diene

at
H
The exo and endo-cycloaddition from the reaction between
H Bonding cyclopentadiene products are shown here.

M
H interaction
H
Dienophile O O
H
H
CN
plane
ed + O H O
ht
LUMO O
Bonding NC of dienophile Cyclopentadiene H
interaction O
ig

Maleic exo-Bicyclo[2.2.1]hept-5-ene-
anhydride 2,3-dicarboxylic anhydride
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A suprafacial [4π + 2π] cycloaddition


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In the aforegiven reaction, the stereochemistry of the O


H
dienophile is retained in the product. H
-C

+ O O
Similarly, when s-cis conformer of (2E,4E)-2,4-dimet-
rhylbuta-1,3-diene is made to react with acraldehyde then the Cyclopentadiene O
O
stereochemical aspect of the diene is retained in the product. O
Maleic
w

This is shown here. endo-Byclo[2.2.1]hept-5-ene-


anhydride
2,3-dicarboxylic anhydride
ie

Me Me
CN CN
ev

One of the factors that give predominant endo-addition


+ is that the transition state is further stabilized by secondary
Pr

Vinyl cyanide orbital interaction by the non-bonding orbital lobes of same


Me Me sign in the frontier molecular orbitals. This is shown here.
s-cis conformer adduct
of hexa-2,4-diene HOMO
of diene
Bonding
Diene plane overlapping
HOMO
of diene Secondary Bonding
overlapping over
H ( ) lapping
Me Bonding O
H interaction ( )
H O
Dienophile
Me H plane LUMO
H of dinophile
CN Bonding
LUMO overlapping
Bonding NC of dienophile
interaction (endo-approach) (exo-approach)

Because of the secondary overlapping, as shown here, activa-


A suprafacial [4π + 2π] cycloaddition tion energy for its formation is less and consequently the rate of

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356 Problems and Solutions in Organic Chemistry

reaction is faster, but the product is less stable due to steric inter- according to FMO theory, this supra-supra cycloaddition can
action. Therefore, if the reaction is allowed to attain an equilib- occur involving HOMO of diene and LUMO dienophile and
rium condition at an elevated temperature, the endo-compound vice versa. These are shown here.
is gradually converted into more stable exo-compound having
no steric interaction. Thus, endo-compound is kinetically (rate)
controlled product and exo-compound is thermodynamically
(equilibrium) controlled product. HOMO of
diene
The exo- and endo- adducts can be chemically distinguished Bonding
by hydrolysis to the corresponding dicarboxylic acid followed ∆E = 10.6 eV overlapping
Bonding
by iodolactonization. Acid from endo-adduct undergoes facile overlapping X
iodolactonization but that from exo-adduct does not. LUMO
of dinophile
H
H O

O X

l
O

ia
H3O+
Diels–Alder adduct

er
H I2 H
H O

at
I H
+ O
NaHCO3

M
OH CH2Cl2 O− LUMO of
H O O −
O O
diene
Bonding
Indolactonization Work-up
ed
∆E = 11.5 eV
Bonding
overlapping X
overlapping
ht
I H
HUMO
H O
ig

H of dinophile
yr

O O OH
Iodolactone
op

X
O
-C

O Diels–Alder adduct
H
H O
It is evident from the aforegiven orbital interactions that
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H3O+
both are supra-supra cycloadditions leading to the formation
ie

O O of cyclohexene derivative. However, energy wise, it has been


I
O−
ev

OH I2 H observed the energy difference (∆E) between HOMO of diene


H H O− and LUMO of dienophile is 10.6eV and that of LUMO of
OH NaHCO3 H
Pr

CH2Cl2 H diene and HOMO of dienophile is 11.5 eV. Therefore, diene-


H O I O
HOMO and dienophile-LUMO interaction in Diels–Alder
reaction is more effective.
O
I 13.12 Explain why [1,5] sigmatropic H-shift in pen-
H OH
H OH ta-2,4-diene is very facile but [1,3]- sigmatropic H shift is
H not observed.
I H O Ans In case of H-shift in penta-2,4-diene, we can consider the
Diiodo compound reaction as the migration of a proton (H+) from one end of the
(No lactonization)
penta2,4-dienyl anion to the other end.
13.11 Show that in case of Diels–Alder reaction, interac-
tion of HOMO of diene and LUMO of dienophile is ener-
getically more favourable than that of the LUMO of diene − + + −
H H H
and HOMO of dienophile.
Ans It is confirmed that Diels–Alder reaction is a supra-su- The interaction of LUMO of H+, an empty 1s orbital, with
pra cycloaddition between a conjugated diene component and HOMO of the conjugated π-system controls the stereochem-
a activated compound having an olefinic double bond. Now, istry of the migration.

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Pericyclic Reactions 357

This is shown as follows. anion. Here LUMO of the alkyl cation (an empty p-orbital)
interacts with HOMO (Ψ2) of an allyl anion.

R3

.
HOMO (Ψ3) of + R1 LUMO of cation
+
peta-2,4-dienyl anion R2

H (6πe system) Antibonding


+ overlap −
LUMO of H (1s) HOMO of allyl anion
(4πe system)
This shows that bonding overlap is possible through supra-
facial migration and this migration does not involve any dis- R1

.
+
tortion or strains in the concerned molecule. Therefore, [1,5] LUMO of cation
sigmatropic H-shift is relatively common. Bonding overlap R2 R3 Bonding overlap

In contrast, the [1,3] sigmatropic H-shift involves the HOMO of allyl anion
HOMO of allyl anion and LUMO of H+. This migration, (4πe system)
shown as follows, requires antarafacial interaction.

l
ia
− From the orbital symmetry, it is evident that HOMO-
HOMO (Ψ2) of allyl anion
LUMO interaction with retention of configuration is symme-

er
+
H (4πe system)
try forbidden.
1s

at
+ If migration occurs with inversion, however, the HOMO-
LUMO of H
LUMO interaction is symmetry allowed.

M
[It is to be noted here that it is the node in the p-orbital
Although the migration is allowed by selection rule, it
(LUMO) that makes the [1,3] suprafacial migration of carbon
is not feasible for excessive strain involved to bridge oppo-
site lobes by migrating proton. Twisting of allyl system, if
allowed, will cause loss of conjugation with the p-orbital of
ed
possible. Each of the two lobes of the p-orbital, which have
opposite phases, is capable of overlapping with each end of
ht
the allyl π-system. Since in II, a bond is broken at one side of
the central atom. For these reasons, concerted [1,3] sigmat-
the migrating carbon and formed at the other side, inversion
ig

ropic H-shift, although allowed by FMO theory of pericyclic


of configuration is observed. In the migration of hydrogen, the
reactions, is not observed.
yr

orbital of LUMO is a ‘1s‘orbital, which has no node. Hence,


[It should be noted that sigmatropic rearrangements (peri-
[1,3] suprafacial migration of hydrogen is not allowed].
op

cyclic reactions) are concerted and do not involve free ions, but
orbital interactions are easily understood if we think in terms 13.14 Carry out an orbital symmetry analysis to show
-C

of ions. In the aforementioned examples, the H-shift may also that thermal suprafacial [1,5] carbon migration should
be considered as radical shift or H− shift across a penta-2,4-di- take place with retention of configuration of the migrating
enyl cation without any change in the final outcome]. centre.
w

13.13 Show that orbital symmetry allows suprafacial [1,3]- Ans A [1,5]-suprafacial sigmatropic rearrangement can be
ie

shift of a carbon centre with inversion of configuration. compared with migration of a carbocation across the ends of
a pentadienyl anion.
ev

Ans Suprafacial mode of [1,3]-shift of a suitably substituted


alkyl group representing a chiral centre can occur either with Pentadienyl anion HOMO
Pr

retention or with inversion of configurations as given here.


1 + +
2
R − C C −
R
3
Suprafacial [ 1,3] C C
R 3
C
shift R Carbocation LUMO
C 1 2
R With retention R
In case of thermal transformation, in the transition state, the
I HOMO of pentadienyl anion interacts with the LUMO of the
1
migrating carbon. Now, the HOMO of pentadienyl anion is
Suprafacial [1,3]
R ψ3 MO having symmetry plane. The required HOMO–LUMO
R
2
R
3 shift 2
C
interaction can be shown as follows.
R
C With retention 3
1 R
R
II (6πe system)
HOMO (Ψ3)
Orbital symmetry relationship of the each migration can be Bonding overlap Bonding overlap
shown as follows, assuming that migration is equivalent to an + LUMO of a carbocation
alkyl cation, which is migrating between the ends of an allyl

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358 Problems and Solutions in Organic Chemistry

Orbital interaction shows that suprafacial mode of [1,5] shift Bonding interaction
of carbon with retention of configuration is symmetry allowed.
H
Empty π* : C Filled sp2
13.15 Show by FMO approach the photochemical orbital H
[1,5]-shift of a chiral carbon centre with inversion of
configuration. LUMO HOMO
of alkene of carbene
Ans This can be shown by analyzing the reaction involving a
Antibonding
migration of a chiral centre involving pena-1,3-diene system.
interaction
The reaction is carried out photochemically involving 4n + 2
number of π electrons where n = 1. According to selection rule
It is obvious from the aforegiven diagram that direct
of photochemical [1,5]-sigmatropic shift, this photochemical
approach of HOMO of alkene/LUMO of carbene or LUMO
reaction can be considered as an interaction between LUMO
of alkene/HOMO of carbene occur then there is always an
of pentadienyl anion and HOMO of a cationic carbon (see
antibonding interaction and cyclopropane ring formation is
Q. No. 13.13). This can be shown as follows.
impossible. However, bond formations become possible, if
carbene approaches the alkene ‘sideways-on’ manner. These
LUMO (Ψ4*) can be shown as follows.

l
of pentadienyl

ia
Photochemical
anion
C y x Bonding interaction

er
x z Bonding Bonding
overlap overlap H H
y

at
z Empty π C Empty p-orbital
HOMO of a carbocation orbital H

M
HOMO LUMO
of alkene of carbene
Migration with
inversion of
ed Bonding
interaction
ht
C configuration
z x of the chiral centre
y Bonding interaction
ig
yr

13.16 An olefinic system readily reacts with singlet car-


Orbital π* C Filled sp2
bene to form cyclopropane system. Explain the reaction in
op

H H
terms of FMO theory. What is the name of such reactions?
LUMO HOMO
Ans The HOMO and LUMO of singlet carbine are shown of alkene
-C

of carbene
here.
Bonding
H interaction
w
:

H
H H
ie

From the aforegiven HOMO/LUMO interactions, it is found


HOMO of carbene LUMO of carbene
that alkene and carbene can readily form cyclopropane deriv-
ev

with two electrons in sp2 with empty p-orbital


ative depending on the trajectory of approach (sideway-on).
The aforegiven reaction belongs to the pericyclic class of
Pr

When a singlet carbene reacts with an alkene in a cycload- reactions and is specifically known as ‘cheletropic reaction’.
dition reaction, it must obey the rules of orbital symmetry. It is a type of cycloaddition reaction in which one of the react-
We might consider two different types of reaction between ing species or fragments acts through a single atom possessing
carbene and an alkene on the basis of FMO theory. These both filled and empty orbital.
are, HOMO of carbene combines with LUMO of alkene and
LUMO of carbene interacts with HOMO of alkene. These are 13.17 Discuss the products and stereochemistry of the fol-
shown as follows. lowing reactions.

(a) O
Bonding interaction Ph
+ O ?
Filled π H Ph
C Empty p-orbital O
orbital
H
(b) O
HOMO LUMO Ph
of alkene of carbene ?
+ O
Antibonding Ph
interaction O

PSOC_Chapter 13.indd 358 8/14/2014 2:54:04 PM


Pericyclic Reactions 359

(c) CO2Me (c) The course of the reactions is shown here.


C H
C ∆
A (C8H10)
∆ CO2Me
A (C8H10) B (C14H16O4) Disrotatory H
ring closure (1R,6S)-Bicylo[4.2.0]octa-
(4n + 2π) electron system 2,4-diene
CO2Me CO2Me
+ H
CO2Me C 4s + 2s
+ CO2Me
C Diels–Alder
Ans H CO2Me CO2Me
(a) Initially the bicyclic compound undergoes thermal con- B (C14H16O4)
rotatory ring opening according to the selection rule for
electrocyclic ring opening comprising 4n electrons (n = 1). retro-Diels–Alder ∆

l
ia
Ph
Ph 4 CO2Me

er
1 5
3 H +
Ph CO2Me

at
2
2
Ph 6 Cyclobutene
1 Dimethyl phthalate
(1R,2S)-diphenyl-1,2- H

M
dihydrocyclobutabenzene (5E,6Z)-5,6- 13.18 The following compound, known as a-phellandrene,
dibenzylidenecyclohexa-
1,3-diene
ed
racemizes when heated. How can you explain this?
CH3
ht
The product from the aforegiven reaction then reacts
with maleic anhydride to form the corresponding Diels– (±)-compound
ig

Alder adducts. Since low temperature gives endo adduct


yr

as the major product, this is only shown here. H


Active
op

Ph Ph
H O Ans Racemization occurs through a reversible suprafacial
H 4s + 2s [1,5]-sigmatropic hydrogen shift. Chiral centre is not involved
-C

R
Ph O in this reaction.
Cycloaddition R
CH3 CH3
O H H O 3 3
Ph
w

Maleic anhydride 2 4 [1, 5]-H shift 4 2


O H
endo-approach Diels–Alder adduct H
ie

5 5
O H 1 1 H
6 H 6 H
ev

Active Active
(b) Similar type of reaction also takes place here, but the (A) (B)
Pr

stereochemical outcome is different.


A and B are enantiomers. Since the reaction is reversible,
Ph at equilibrium, racemic mixture is obtained.
4
1 Ph 5
3 H 13.19 Indicate the type of sigmatropic shift in the follow-
2 H ing transformation.
2
Ph 6
1 Me
(1R,2R)-diphenyl-1,2- Ph Me
dihydrocyclobutabenzene (5E,6E)-5,6-
dibenzylidenecyclohexa-
1,3-diene
Me Me
Ph Ph
H O Ans One [1,5]-sigmatropic carbon migration followed by
H 4s + 2s two [1,5]-hydrogen shifts are necessary for this transforma-
R
H O tion. Carbon migration occurs with retention of configuration
Cycloaddition S
and, therefore, this is suprafacial interaction between con-
O Ph H O
Maleic anhydride Ph cerned HOMO-LUMO. The [1,5]-hydrogen shifts can also
O endo-approach be suprafacial according to selection rules for sigmatropic
Diels–Alder adduct
O rearrangement.

PSOC_Chapter 13.indd 359 8/14/2014 2:54:09 PM


360 Problems and Solutions in Organic Chemistry

Me (a)
Me 5 H 150° C
5
[1, 5] C- shift ?
4 1
4 O
1 2
3 3
2 (b)
Me Me
65° C
?
[1, 5] H- shift O

Me Ans Both are intramolecular Diels–Alder reactions. The


H Me
1 2
mechanism of the reactions can be shown as follows.
[1, 5] H- shift 5
5 (a) 7 6 4
3 150° C
4 8 3
Me Me O 9 10 2
1
It should be noted here that the aforementioned sigmat- O O
ropic shifts should not be considered as 1,2-shift because con-

l
(c)

ia
jugated system is to be considered to give (1, j)- system of
nomenclature.

er
O
13.20 Predict the structure of the following Diels–Alder

at
O
reaction.
65° C

M
OMe
CO2Me 5
? 6

Me3SiO
+
ed 8
7 4
3
ht
9 10 2
Ans The diene part is electron rich and its HOMO is used 1
ig

in the cycloaddition. It will react with LUMO of alkene, un O


α,β-unsaturated ester. [4π + 2π] cycloaddition can be shown
yr

In the aforegiven (a) intramolecular cycloaddition reac-


as follows. tions, two new rings have been formed. The six-membered
op

OMe MeO CO2Me ring containing a cis-alkene and its formation does not pose
MeO2C
any problem, and the ten-membered ring with the trans-alk-
-C

+ ene is definitely a problem.


Me3SiO Me3SiO In case of the second problem (b), the presence of benzene
4π 2π ring makes the reaction to some extent strain free. Resonance
Work up
w

associated with the benzene ring in the second compound


ie

CO2Me lowers the energy of the LUMO of the alkene part. That is
why the second reaction occurs at a faster rate.
ev

13.22 Suggest a mechanism for the following transforma-


Pr

O tion.
The stereochemical aspect of this cycloaddition reaction O
OH
can be shown as follows. In alkene, H and CO2Me is cis and
that has been retained in the product and endo approach is pre- O + O
ferred so that the ester group becomes tucked underneath the
diene so that it can have secondary overlap with the orbitals O
of the of the middle two atoms of the diene part. The stereo- O
chemistry of the OMe group comes from endo attack. O −
O MeO O
OMe MeO CO Me CO2OH MeOH
2 CO2Me
MeO2C O
CO2H
H
Me3SiO H Ans The first step of the reaction is Diels–Alder reaction. This
Me3SiO O
Endo attack H is followed by reaction between the free OH group and the
H
anhydride carbonyl group leading to the formation of a lac-
13.21 Give the products of the following reactions and tone along with a free CO2H group. The second step seems
comment on their rates of reactions. to be base catalysed enolization followed by the opening of

PSOC_Chapter 13.indd 360 8/14/2014 2:54:14 PM


Pericyclic Reactions 361

the epoxide bridge. Subsequent decarboxylation leads to the


desired compound, through the loss of bridging oxygen, pre- hν
sumably as water (E1CB). The total mechanism of the reaction Photochemical
can be shown as follows. H N H H H
N

H CO2Et CO2Et
O Only terminal p-orbitals shown (C)
OH O .. :
O (Disrotatory movement of the orbitals)
O
O + O O
In case of the product (B), bicyclic system is formed by
O
O thermal disrotatory ring closure involving six π-electrons, that
is, (4n + 2) electrons. This is allowed electrocyclic ring clo-
O O
O O sure according to FMO approach.

O O

O H
O H
− H O Heat
MeO H O
N

l
H N

ia
O H
O O CO2Et
− CO2Et

er

O −
O O
CO 2
− O H
H

at
O
MeOH Thermal

M
O − H N
MeO N
HO

O
C
O

O
HO −
O

O
ed CO2Et
Only terminal p-orbitals shown
H
CO2Et
ht
CO2 (Disrotatory movement of the orbitals)
ig

13.24 Give the explanation of the following sequence of


yr

O reactions.
op

CO2H O CO2H
-C

13.23 Give the explanation of the following eletrocyclic


ring closure based on FMO approach. CO2Bu
CO2H O
w

H
R3N
A + B + O
ie

hν Heat
CO2Bu
ev

.. N CO2Bu
H N H H N H H
CO2Et
Pr

CO2Et CO2Et (B) Ans The first step of the reaction is four electron conrota-
(C) (A) tory electrocyclic ring opening. Two different conrotatory
movements leading to the formation of two diastereoiso-
Ans The compound (A) undergoes photochemical electrocy- meric dienes. One of the dienes, on being treated with R3N:
clic ring closure involving eight π-electrons (4n) of four ole- undergoes intramolecular ring closure but the other does not.
finic double bonds. The lone pair of electrons on the nitrogen Therefore, finally we get constitutionally different products.
atom is not involved in this electorcyclization. According to Total mechanism can be shown as follows.
FMO theory, photochemical electrocyclic reactions involving
CO2H CO2H
(4n) π-electrons should be disrotatory and the stereochemistry CO2H
is determined by the LUMO. The disrotatory ring closure can +
be shown as follows. CO2Bu
CO2Bu CO2Bu
Four electrons (A) (B)
hν conrotatory
electrocyclic Conrotatory Conrotatory
H H ring opening
H N H N
BuO2C CO2H BuO2C CO2H
CO2Et CO2Et
(C)

PSOC_Chapter 13.indd 361 8/14/2014 2:54:19 PM


362 Problems and Solutions in Organic Chemistry

2 +
1 O O H
3 CO2H +
4 R3N: −
O −R3NH H
+
5 O
6 OBu
CO2Bu H H
O OBu +
(B) R3 N H − HO : ..OH
O
(2Z,4E)-isomer

O
OBu H
OH : OH
+
O
13.26 Give the final product of the following reaction with
− + explanation.
CO2H O O R3NH
C Me

l
ia
R3N: No further reaction Me Heat
?

er
CO2Bu CO2Bu
(A)

at
Ans The reaction involves to [1,5] shifts. The first one is [1,5]
(2E,4Z)-isomer shift of ring carbon and the next one is [1,5]-shift of hydro-

M
gen. The migration of the ring carbon is stereospecific with
13.25 How can you explain the following transformation. the retention of configuration. The overall reaction can be
Why does compound (A) fail to undergo spontaneous aro-
matization? However, the compound aromatizes when
ed
shown as follows.
Me Me
ht
treated with acid. Offer an explanation. 2 [1,5]-shift 3
3 2
Me 1 of a bond
ig

H 1
4
yr

+ 4
H Heat H 5 5

Suprafacial H
op

with retention Me
OH OH Me [1,5]-
OH
-C

(A) hydrogen shift

Ans The first step of the reaction is Cope rearrangement which


w

is a [3,3]-sigmatropic rearrangement. The rearrangement is


facilitated due to the strain of the cyclopropane ring system. Me
ie

Final product
ev

H
1 13.27 Give the product of the following reaction of the hep-
2
H Cope tafulvene and comment on the stereochemistry of the product.
Pr

1
2 Rearrangement
(NC)2C = C(CN)2
3
3 H + ?
OH HO
(A) TCNE
Heptafulvene
The compound (A) cannot go directly to an aromatic sys- Ans The aforegiven reaction [14 + 2] is a cycloaddition
tem because that would require a [1,3]- hydrogen shift and reaction. The product is shown here.
that must be antarafacial, but due to the rigidity of the ring
system, this is not facile.
H
3
2 H
[1,3]-H shift
NC CN
1 (NC)2C = C(CN)2 NC CN
H
HO OH The stereochemistry of the product shows that the alkene
has added in a trans mode to the heptafulvene. To achieve
However, on treatment with acid, the compound (A) under- this geometry, a twisted or mobius type cyclic arrangement of
goes aromatization through an ionic mechanism as shown the sixteen participating π-electrons must be involved. This
here. [14s + 2a] or [14a + 2s] cycloaddition reaction provides an

PSOC_Chapter 13.indd 362 8/14/2014 2:54:24 PM


Pericyclic Reactions 363

example of a [4n] stabilized transition state. In fact, a twisting 1 2


10 3
of the heptafulvene molecule about the central double bond Heat
H H 9 4
allows this reaction to occur antarafacially. Consequently, the
8
product has trans stereochemistry. The shape of the reactants A B 7 5
6
enables this [4n] Möbius transition state to be formed. Möbius Disrotatory allowed
thermal ring opening Because of large ring,
type reactions do not provide smaller rings. it is almost planar and
therefore does not
13.28 Predict the product of the following reaction. violate Bredt’s rule.

The large ring in the compound B is nearly planar and


? should show aromatic character.
Me O
13.31 Which of the following electrocyclic reactions
Ans It is a case of [3,3]-sigmatropic rearrangement (Claisen should occur readily by concerted mechanism?
rearrangement). The final product is a cyclohexene derivative.
H
The course of the reaction can be shown as follows.
Heat
Me Reaction: (1)

l
O ,
[3,3]-sigmatropic

ia
3 rearrangement
H

er
1 3
Me O H
Me 2 O 2

at
1 Me Me
Me Heat
Reaction: (2)

M
13.29 The following compound is formed again in an
Claisen type rearrangement. Show the reactions. H
ed
Ans The reaction (1) is a case of thermal electrocyclic ring
ht
closure involving 6π electrons, that is, (4n + 2) system.
Therefore, the reaction should be disrotatory. The reaction is
ig

14
CH2 =CH =O
thermally allowed and rate of the reaction would be faster.
yr

Ans If we carry out the following reverse Claisen rearrange-


op

ment then we get the desired compound. Both backward and HOMO of triene system, only the
forward reactions can be shown as follows. terminal orbitals have been shown
-C

2
3 Disrotatory H
ring closure
1 Heat
w

1 2 3
CH2 – CH = O
ie

14 H
ev

1 2 3 In case of the reaction 2, stereochemistry of the trans prod-


O – CH= CH2
uct suggests that the ring closure should be antarafacial (con-
Pr

1 14

2
[3,3]-sigmatropic rotatory) because it is a case of (4n + 2) π-system and it should
3 be done photochemically. In this case LUMO of triene system
CH2– CH = O
14 should take part. Since here the reaction has been done ther-
mally, the reaction would occur much slowly.
13.30 Identify the hydrocarbon ‘B’ and the intermediate
‘A’ in the following reaction sequence. The compound ‘B’
LUMO of triene system
is formed from ‘A’ spontaneously in a pericyclic reaction.
Conrotatory
ring closure H
2Br2 KOH Heat
? A B
EtOH Heat

Ans The course of the aforegiven reactions can be shown as


follows. H
Br Br The trans-junction
2Br2 EtOH shows that ring closure
KOH shoud be antarafacial
Br Br A which is not thermally allowed

PSOC_Chapter 13.indd 363 8/14/2014 2:54:29 PM


364 Problems and Solutions in Organic Chemistry

13.32 Show the reaction of an alkene with a singlet car- HOMO (π-bond) of an alkene
bene in terms of orbital symmetry. (b) Lone pair of carbene in its filled orbital (filled sp2 orbital)
Ans In the case of a reaction between an alkene and singlet HOMO interacts with π* antibonding orbital of the alk-
carbine, two possibilities are there. ene (LUMO). Orbital pictures of these interactions can be
(a) Carbene LUMO (empty p-orbital) interacting with shown as follows.

Bonding interaction Antibonding interaction


Carbene HOMO
Me H Carbene LUMO Me H

H H
Filled π-orbital C Empty π∗ orbital C
H H
Me H Empty Me H
p-orbital Bonding interaction
Alkene HOMO Alkene LUMO
Antibonding

l
interaction

ia
er
It is evident from the aforegiven orbital interactions bonds can be formed if the carbene interacts with the alk-
that the direct approach of the carbene to the alkene does ene in a ‘sideways on’ approach. This is shown here.

at
not lead to the formation of two new bonds. Two new

M
Bonding interaction Bonding interaction

Me H Carbene LUMO
H
ed Me H Carbene HOMO
H H
ht
H
Filled Empty C
C
ig

π-orbital π* orbital
Empty p-orbital
yr

Me H Me H
op

Alkene HOMO Alkene LUMO


Bonding interaction Bonding interaction
-C

Me H
H

H
w

Me H
ie
ev

13.33 Give the products of the following reactions.


(b) H H
1 1 [3,3] sigmatropic
Pr

(a) 2 2

Heat 3 3
?

13.34 The following 1,2-diphenylhydrazine can be con-


(b) H H Heat verted to an indole derivative by the reaction given here.
Propose a plausible mechanism.

Ans Both of the aforegiven reactions are [3,3]- sigmatropic


reactions which are pericyclic reactions and thermally Heat
NH
allowed. Reactions can be shown as follows. N H+ N
H H
(a) Ans The given diphenylhydrazine has the ideal structure to
3 3
undergo [3,3]-sigmatropic rearrangement. In this process
2 2 [3,3] sigmatropic
1 1 N–N σ bond is broken and produces a highly unstable double
imine which when treated with acid is readily converted into

PSOC_Chapter 13.indd 364 8/14/2014 2:54:33 PM


Pericyclic Reactions 365

an indole derivative. The sequence of reactions can be shown FMO approach


as follows.
Ph
3 Ph
3
2 HO2C
[3,3] sigmatropic HO2C
1 NH HOMO
2 N 1 Disrotatory movement
H of terminal orbitals
Disrotatory
H
Aromatization

NH .. NH H H
N N
H Ph
H H HO2C
H+ (A)

H H FMO approach
H+

l
ia
.. + .. Ph
N NH3 N NH2 HO2C
H Ph

er
H HO2C
HOMO
Disrotatory movement

at
H of the terminal orbitals
Disrotatory

M
N+ N
H H
ed H H
Ph
ht
13.35 Two different diastereoisomeric compounds are HO2C
(B)
formed from the following compound when the reaction
ig

is carried out thermally, Explain their formation based Compounds A and B are diastereoisomeric although both
yr

on Woodward–Hoffmann rules of electrocyclic pericyclic of them have cis ring junction


reactions.
13.36 What compound is obtained when the compound B
op

in question 13.35 is heated?


Ph
-C

Ans The compound B (in the above question), on heating


undergoes (4πs + 2πs) cycloaddition reaction known as Diels–
HO2C Alder reaction. The final product is a tetracyclic compound.
w

The course of the reaction is shown here.


Ans The given compound first undergoes 8 π-electron (4n) Ph
ie

conrotatory electrocyclic ring closure. Since it involves 4n


ev

electrons, HOMO with C2 symmetry is involved. Only the ter-


minal orbitals have been shown in the following diagram. A H H
Pr

cyclooctatriene compound is formed having substituents with H H


Ph
trans stereochemistry. The cyclooctatriene then undergoes HO2C
B
6π-electron (4n + 2) disrotatory ring closure, involving HOMO HO2C
Intramolecular
with σ-plane to give two diastereiosomeric bicyclic fused sys-
Diels–Alder
tems. The course of the reactions can be shown as follows. reaction
Ph
H
FMO approach: HO2C Ph H
H
HOMO H H
conrotatory movement
of terminal orbitals
Conrotatory 13.37 Synthesize hexaphenylbenzene using a Diels–Alder
reaction followed by a cheletropic elimination of carbon
monoxide. How would you get the starting cyclopentadie-
none compound?
HO2C Ph Ans The desired compound can be prepared as follows.

PSOC_Chapter 13.indd 365 8/14/2014 2:54:37 PM


CH2 O

+ O

CH2 O
366 Problems and Solutions in Organic Chemistry Diels–Alder reaction
[4π + 2π]
Ph Ph (Contd) Electrocyclic reaction
Ph
O O
C
O + 150°C
C O O
Ph
Ph Ph (A) O (B) O
4π-electro
electrocyclic ring O
Cyclization Diels–Alder [4π + 2π]
opening electrocyclic reaction O
Diels–Alder reaction
O
O O O
Ph
Ph
Ph Chelectropic Ph Ph O O
Ph reaction
−CO Ph Ph O (C) O
Ph Ph +
Ph Ph H3O
Bicyloc[2.2.1]heptadiene-7-one HO2C CO2H
Hexaphenylbenzene

l
derivative

ia
(Diels–Alder adduct)
HO2C

er
(D) CO2H
The staring cyclopentadienone compound can be easily

at
obtained from base catalysed condensation between diben-
13.39 Which of the following retro-Diels–Alder reactions
zylketone and benzoin.

M
will take place most easily? Which one will be the most
O difficult? Give reasons.
Ph

Ph
CH2

C
C
+
CH2 Ph

C
(a) ed
ht
Ph +
O O
ig

Base
(b)
yr

H O H O +
op

Ph Ph Ph Ph
(c)
-C

Ph Ph
Ph Ph +
HO OH

Ans The reaction shown in (c) will occur most rapidly because
w

13.38 What are the compounds A, B, C and D in the fol-


the aromatic stabilization of benzene is gained. The reaction
ie

lowing sequence of reactions.


(b) would be most difficult because one of the products is a
O
ev

CH2 very unstable cyclobutadiene with anti-aromatic property.


Room temperature 150°C The reaction (a) would be less rapid than (c) but more rapid
+ O A B
Pr

than (b).
O O
CH2 13.40 The aliphatic Claisen rearrangement, a [3,3]-sig-
O matropic rearrangement, involves a ‘chair like’ transition
O state, as depicted here.
H 3O + O O O
D C
Ans The course of the reaction can be shown as follows. (a) On the basis of the given transition state, show which
CH2 O one, A or B, would be the major product in the follow-
ing rearrangement.
+ O
O O
O ∆ +
CH2 O H H
H3C (A) (B)
Diels–Alder reaction
[4π + 2π] (b) What products would you expect from the Claisen
Electrocyclic reaction rearrangement of the following of the following enol
O O ethers?
(Contd)
150°C
O O

(A) O (B) O
4π-electro
electrocyclic ring O
[4π + 2π]
opening electrocyclic reaction
PSOC_Chapter 13.indd 366 O 8/14/2014 2:54:42 PM
Diels–Alder reaction
Pericyclic Reactions 367

(i) O (ii) O H
H O H3C O
Me H
Me S Chair-like
Ans
(S,E)-4-(Vinyloxy)hexpent-2-ene transition state
(a) This compound has a chiral centre and can have two
diastereoisomeric chair-like transition states to undergo
Claisen rearrangement.
H
H H O
(A) H3C O (B) O S O
H
CH3 CH3
(S,E)-3-Methylhex-4-enal
The reactions are shown here.
13.41 (a) What happens when cyclopentadiene is heated.
H H
1 1 2
Do you expect similar reaction when cyclopentadiene is
H3C O H3C

l
O made to react with ethylene?

ia
3
2
3 (b) Between cyclopentadiene and buta-1,3-diene, which
Chair-like

er
[3,3]-sigmatropic one will react more rapidly as a dienophile in Diels–
transition state
rearrangement
Alder reactions? Give your reasoning.

at
Ans

M
O H (a) In this case, Diels–Alder reaction takes place where one
H3C O molecule of cyclopentadiene participates as conjugated
H
(E)-Penta-4-enal
ed
diene and the other as dienophile. The reaction is shown
here.
ht
H 1 H
2 1 O O
3 +
ig

3 2
CH3 Diene Dienophile Diels–Alder adduct
yr

CH3
Chair-like
[3,3]-sigmatropic
transition state
op

rearrangement
-C

H H
H +
O H O
H
w

H Endo-product
(Z)-Pent-4-enal Exo-product
CH3
ie

Cyclopentadiene, in this case, can also function as a


ev

The rearrangement by the first chair-like transition dienophile. This is because of the fact that due to cyclic
state is preferred because the methyl group is in equatori- structure with two olefinic double bonds, it is a strained
Pr

al-like orientation, rather than axial-like orientation in the molecule and its reaction will require less activation
other transition state which leads to the formation of the energy to participate in Diels–Alder reaction. In case of
(Z)-isomer. ethylene, the molecule is very stable and require large
(b) The products from the Claisen rearrangement of the two amount of activation energy to react as a dienophile.
compounds shown in the problem are given here. That is why unsubstituted ethylene does not participate in
Diels–Alder reaction. When some electron withdrawing
O O group like –CH=O or –CN is attached to the sp2 carbon
of ethylene then Diels–Alder reaction becomes facile.
Chair-like (b) It is a fact that conjugated diene part in a Diels–Alder
(E)-1-((E)-Prop-1-1enyloxy)but-ene transition state
reaction must react in its s-cis conformation (s–single
bond) for the effective overlapping of its HOMO orbital
H with that of LUMO of dienophiles, when they come
S
H closure. Now in case of cyclopentadiene, conjugated
O CH3 O diene-system is already cis-locked and consequently at a
H higher energy state to react quickly.
R
CH3 In case of buta-1, 3-diene, the s-trans-conformation is
(2S, 3R)-Pent-4-enal more stable than the s-cis-conformation. So it needs more

PSOC_Chapter 13.indd 367 8/14/2014 2:54:47 PM


368 Problems and Solutions in Organic Chemistry

activation energy to covert itself to the necessary s-cis [It should be noted that after thermal conrotatory ring
conformation, which then can react. This why buta-1,3-di- opening of cis and trans isomers of 3,4-dimethylcyclobu-
ene is less reactive than cyclopentadiene as diene in Diels– tane, we get open chain hexa-2,4-diene. When photochemi-
Alder reaction. This is shown in the following diagram. cal ring closure is carried out on these hexa-2,4-dienes, then
the LUMO (ψ*) takes part in the reaction. These have been
shown in the aforegiven diagram]. Overall reactions can be
shown as follows.
Cyclopentadiene Buta-1,3-diene Buta-1,3-diene H
The structure is almost stable s-trans less stable s-cis CH3
rigid and the double conformation conformation ∆ CH3
(2Z,4E)-
bonds are s-cis-locked H Hexa-2,4-diene
cis-3,4- CH3 hν
CH3
13.42 How can you transform trans-3,4-dimethylcy- Dimethylcyclobutene
clobutane to cis-3,4-dimethylcyclobutene and vice-versa. hν CH3
Explain your answer. CH3
∆ H (2E,4E)-
Ans The structures of cis- and trans-3,4-dimethylcyclobutane

l
H Hexa-2,4-diene

ia
are given here. CH3
CH3 CH3 trans-3,4- CH3

er
Dimethylcyclobutene

at
CH3 CH3
13.43 Give the mechanism of the following conversion.

M
cis-3,4-Dimethylcyclobutene trans-3,4-Dimethylcyclobutene
CH3 CH3
Each can be converted into the other by carrying out ther-
mal ring opening followed by photochemical ring closure.
Both ring opening and ring closure reactions in these cases
ed O
10 0°C
D 2O O
ht
are 4n electron manipulations and consequently thermal pro- H3C CH3 CD3
H3C
cess of ring opening is conrotatory and photochemical ring
ig

closure is disrotatory. Thus interconversions of cis isomer to Ans It is a case of repeated [1,5]-shift of hydrogen, replace-
yr

trans isomer and vice versa can be done as follows. ment of hydrogen atom by deuterium and then tautomeriza-
op

tion. The course of the reaction is shown here.


CH3 H H ∆
H Me CH3 CH3
-C

Conrotatory Me H
Me Me ring LUMO of diene
CH3 opening
cis isomer ..
cis-3,4-Dimethyl conrotatory O O:
w

Disrotatory
cyclobutene ring opening ring closure
H3C CH3 H3C CH2 H
ie


[1,5]-shift
ev

H Me CH3
Pr

Me CH3 CH3 CH3


H CH3
trans isomer
trans-3,4-Dimethy D 2O
lcyclobutene 100°C O
O O
H3C CH2 H H3C CH2
D
H3C CH2D
CH3 Me H ∆
Conrotatory Me Me Repeat
CH3 H Me ring H H
trans-3, trans isomer opening LUMO of diene CH3
conrotatoryring
4-Dimethyl opening Disrotatory
cyclobutene ring closure
hν O

Me Me CH3 H3C CD3

H H CH3 13.44 A chiral compound, hexa-1,5-dien-3-ol on heat-


trans isomers cis-3,4-Dimethyl ing gives an achiral aldehyde. Identify the aldehyde and
cyclobutene explain the reaction.

PSOC_Chapter 13.indd 368 8/14/2014 2:54:51 PM


Pericyclic Reactions 369

Ans The reaction is a case of [3,3]-sigmatropic rearrange- (b) Mg MgCl


ment. The rearrangement is shown here.
2
65°C
HO 1
3
MgCl
Cl
OH 3
1
Hexa-1,5-diene-3-ol 2
H CO2 H
(Chiral molecule) COOH
[3,3]-sigmatropic H3O+ MgCl

HO
H H
O H
(c)
O O H O
H
H
O Heat
Hex-5-enal

l
The parent compound has one chiral centre and, therefore, (d) H O

ia
is optically active. The rearranged product is hence an achiral

er
molecule. H

at
13.45 Give the mechanism of the following
transformations:

M
(CH3)2AlCl CH3CH=O
(a) SOCl2 CH2Cl2(Soln)
+ SO2

OH
Cl ed OH
ht
(b) CO2H
Mg CO2
ig

65° C H3O+
Cl (e) H2C
yr

CH2
450°C H2C
(c) O H
op

O H2C H
H CH3 H H3C
-C

The last example is a case of intramolecular ene-reaction.


(d) OH 13.46 (a) Show the three different types of possible intra-
w

CH3CH = O molecular ene-reactions.


ie

(CH3)2AlCl (b) Give the plausible mechanism of each of the following


CH2Cl2(Soln) transformations and recognize the type of ene-reac-
ev

(e) tion involved.


H2C CH2
Pr

(i) H
H2C H3C 300°C
CH3 CH3

Ans The mechanism of each of the given transformations is CH2 O OH


given here.
(a) (ii) C
SOCl2 H2

OH O Cl C
S H2
O 350°C
H H2 H
[1,5]-shift C

+
+ SO2
Cl C
H2 H H

PSOC_Chapter 13.indd 369 8/14/2014 2:54:58 PM


370 Problems and Solutions in Organic Chemistry

(iii) H3C CH3 Ans The mechanism of the given transformation can be shown
380°C CH3
as follows.
Ph CH3 H
O O O H H
H H3C
Ph
Ans
(a) Three possible modes of intramolecular ene reactions are 100°C
shown here.
Ph
X X X Z
H CH3
Y Z Y Z Y
H H Since ene reactions usually involve coupled bond-making
Tyoe-I Type-III
Tyoe-II and bond-breaking operations associated with short π-elec-
tron systems (2 or 3 carbons), their stereospecificity is almost
X X Z always suprafacial with respect to both components.
X H

l
Z

ia
Y Y 13.48 Give the mechanism of each of the following trans-
Z Y
H

er
H formations and identify the type of pericyclic reaction
(b) The mechanism of the aforegiven transformations is given involved.

at
here. (a) CH3 CH3

M
(i) CH2 Heat
H O Ph
300°C N
CH3
Type II
H ene-reaction H2C OH
ed
H
C
N
+

O−
H
ht
CH2 O
Ph
ig

(ii) H (b) OH
H O
yr

CH
350°C KH, THF
H
op

Type III Heat


C ene-reaction C
H2 H2 H H
-C

H2 H
Ans
C (a) It is a case of [3,3]-sigmatropic rearrangement involv-
CH2 350°C
w

ing six electrons. The rearrangement can be shown as


Again H Type III follows.
ie

C ene-reaction 3 CH3
(i) CH3
H H
ev

Heat
2 O
H2
1 Ph
(iii)
Pr

H2C
1 N
C H N +
H 380°C C 2 O
− H
3
Type I O Ph
O H
[3,3]-sigmatropic rearrangement in this case takes place
suprafacially with retention of configuration.
CH3 CH2
(b) It is also a case of [3,3]-sigmatropic rearrangement. The
CH3 necessary mechanism is shown here.
CH2
O O O CH2 − 2 −
O H H 3 1 O
H H O

13.47 Give the mechanism of the following transforma- KH, THF 3

tion with the necessary explanation. 2 1


[3,3]-sigmatropic H
Ph Ph
rearrangement
H 100°C
CH3 13.49 How many products are formed when cis- and
H
trans-but-2-ene are made to undergo photochemical [2s

PSOC_Chapter 13.indd 370 8/14/2014 2:55:04 PM


Pericyclic Reactions 371

+ 2s]-cycloaddition separately and also between cis and Ans In this case a normal Diels–Alder reaction is followed
trans isomer. Give reasons for your answer. by a reverse Diels–Alder reaction. The driving force for the
Ans Four different diastereoisomeric 1,2,3,4-tetramethylcy- reverse Diels–Alder is the formation of a product that is stabi-
clobutanes are possible. Each of the pure alkene stereoisomers lized by aromaticity. The course of the reaction is shown here.
can undergo an allowed photochemical [2s + 2s]-cycloaddi- CO2Et
tion in two distinguishable ways. cis-But-2-ene reacts to give
compounds A and B, trans-but-2-ene reacts to give com- H3C C
+
pounds B and C; and the mixture of cis- and trans-but-2-en- C
ecan give these compounds plus a fourth one, compound D, CO2Et
that results from the [2s + 2s] cycloaddition of cis-but-2-ene
Diels–Alder
to trans-but-2-ene. The products are shown here.
EtO2C
H H
H3C H3C EtO2C
C C CH3
H3C CH3
+ EtO2C EtO2C CH3
H H retro-Diels–Alder

l
C C CH3

ia
H3C
H3C CH3 A

er
cis + cis
H3C EtO2C
CH – CH
H H

at
CH2 +
C C H 3C CH3
H3C EtO2C CH3

M
H 3C CH3
+
H3C CH3 13.51 Account for the following thermal transformation.
H 3C
C

cis + cis
C
CH3
H3C B CH3
ed Ph Ph Ph Ph
ht
Heat
H CH3 Ph CD3 H 3C Ph
ig

C C H3C CH3 CH3 Ph Ph D 3C


H
yr

H3C
+
H CH3 Ans This reaction suprafacially appears to involve about
op

C C H3C CH3 both the double bonds, a process that is virtually impossible.
B
H3C H In fact, the transformation can be explained on the basis two
-C

trans + trans conrotatory electrocyclic reactions, the first one is ring clos-
H ing, and the second one a ring opening. The mechanism of the
CH3
C C H3C reaction is shown here.
w

CH3
H3C H
Ph
ie

+ Ph ∆ Ph Ph
H3C H Conrotatory
Ph Ph
ev

C C H3C CH3 Ph CD3


CH3 C Ring closure
H CH3 Ph H3C CD3
trans + trans
Pr

Conrotatory electrocyclic
H H ring closure invoving Conrotatory electrocyclic
H3C 4π electrons, thermally ring opening invoving
C C CH3 4π electrons, thermally
H3C CH3 allowed
allowed
+
H CH3 ∆
C C CH3 Ring opening Contotatory
H3C
H3C H D
cis + trans Ph Ph
13.50 Give the mechanism of the following transforma- H3C Ph
tion. What is the driving force for this reaction to occur?
Ph D3C
CO2Et
H3C EtO2C 13.52 Give the IUPAC name of the following compound.
C
+ What happens when it is heated at an elevated tempera-
C EtO2C CH3 ture of 200oC?
CO2Et +
H3C CH3
CH – CH CH2 H Ph
CH3
H3C H3C

PSOC_Chapter 13.indd 371 8/14/2014 2:55:09 PM


372 Problems and Solutions in Organic Chemistry

Ans The IUPAC name of the given compound is (4S, 6E)-2- However, this type of thermal ring opening does not occur in
methyl-4-phenylocta-2,6-diene. When heated, it undergoes case of the compound (A). The reason that the compound (A) is
[3,3]-sigmatropic rearrangement, which is specifically known inert under the same conditions is that conrotatory ring opening
as Cope rearrangement. The reaction is believed to proceed of (A) would give a stereoisomer of (D) in which one of the
through stable chair-like conformation as transition state. The cyclohexene rings would contain a trans double bond within a
course of the reaction is given here. six-membered ring. This induces so much strain that the reaction
does not occur, even though it is allowed by the selection rules.
CH3 Ph
1
H 8
trans (Twisted)
CH3
H3C 2 4
5
6
7 double bond
3

H
H H H
1 H H
3
2 CH3 Conrotatory
Ph CH3 Ph ring opening
2 CH3 CH3
1 3
H H CH3
CH3 13.54 (a) What happens when the following two diastere-
[3,3]-sigmatropic rearrangement Stable chair-like oisomeric compounds are subjected to photochemical ring

l
transition state

ia
opening?
H H CH3 CH3

er
6
Ph 1
2 3 4
CH2 Ph H
CH3

at
5
H H3C CH3 H H H H
CH3 I II

M
(1E,4S)-3,3,4-Trimethyl-1
-phenylhexa-1,5-diene (b) How can you convert (I) to (II) and vice versa?
(Major product)

H
Diaxial interaction
ed
(i) (ii)
ht
Ph CH3 H H H H
Ph CH3 Flipping A B
ig

CH3 H H
Ans (a) In these two cases, photochemical ring opening takes
yr

H CH3 H3C
CH3 place in disrotatory manner as shown here. The products are
Stable chair-like Unstable chair-like
op

macrocyclic rings with a triple bond and a double bond.


transition state transition state

-C

H CH3 H H (Z )-Cyclodeca-1-en-7-yne
H CH3 Ph (I)
CH2
w

H H Disrotatory
H ring opening
H3C CH3
ie

Ph H3C CH3 hν
ev

(1Z,4S)-3,3,4-Trimethyl-1-
phenylhexa-1,5-diene
(Minor product) H H
Pr

(E)-Cyclodeca-1-en-7-yne
(II)
13.53 Between the following two isomeric compounds, Disrotatory
ring opening
which one will undergo thermal ring opening of the middle
cyclobutene ring. Explain your answer. (b) (I) can be converted into (B) by following sequence of
reactions. (A) is first subjected to photochemical disrota-
(a) (b) tory ring opening to (Z)-cyclodeca1-en-7-yne. This is
then subjected to thermal ring conrotatory ring closure.
H H H H
A Both are allowed by sequence rules for electrocyclic reac-
B
tions involving 4nπ electrons (n = 1).
Ans Between the diastereoisomers (A) and (B), the trans-
fused isomer (B) will undergo thermal conrotatory ring open- hν
ing. This is allowed process based on electrocyclic reactions. Disrotatory
The reaction is shown here. ring opening
H H
(b) (I) (Z)-Cyclodeca-1-en-7-yne
Conrotatory
H H 1,1-bi(Cyclohexene) ring closure ∆
Conrotatory ring opening (C) (Contd)

H H
(II)

PSOC_Chapter 13.indd 372 8/14/2014 2:55:15 PM



Disrotatory
ring opening
H H
(I) (Z)-Cyclodeca-1-en-7-yne
Pericyclic Reactions 373
Conrotatory
ring closure ∆
(Contd)

trans-1,2-Divinylcyclobutane
H H ∆
(II)

Similarly (II) can be transformed to (I) by following


sequence of reactions.
Diradical 4-Vinylcyclohex-1-ene

Conrotatory
ring opening
H H 1,1′-bi(Cyclohexene)
(1Z,5Z)-Cycloocta-1,5-diene
Disrotatory

ring closure (c) The product and mechanism of the reaction is shown

l
here.

ia
H

er
C CH2
C

at
H H
H

M
13.55 Give products of each of the following reactions and (E)-5-Allylidenecyclohexa-1,
explain the reactions. 3-diene (s-trans conformation)
(a)

?
ed H
ht
H
H [1,5]-suprafacial
3
2 C C H
ig

4
(b) ∆ C H-shift C
? 1
yr

H Symmetry allowed CH3


CH2
H 5
(Z)-Prop-1-enylbenzene
op

(c)
∆ (s-cis conformation)
?
-C

13.56 The following conversion cannot occur as a con-


Ans certed pericyclic reaction. Explain.
(a) The product is (1Z,5Z)-cycloocta-1,5-diene where both CH2 CH3
w

the double bonds have cis-geometry. Reaction occurs in


boat-like conformation. Chair-like conformation cannot
ie

be achieved due to steric constraint. 5-Methylenecyclohexa-1,3-diene Toluene


ev

Ans In the above transformation, concerted pericyclic reac-


tion requires [1,3]-antarafacial hydrogen shift. Although it is
Pr

a symmetry allowed process, geometrically it does not occur


cis-1,2-Divinylcyclobutane because it requires excessive twisting of bonds resulting in a
∆ highly strained transition state. That is why, concerted mech-
anism is not possible here.
H
C
H
Boat-like (1Z,5Z)-Cycloocta-1,5-diene
transition state H
H
(b) In this case, the trans-1,2-divinylcyclobutane gives a
mixture of 4-vinylcyclohex-1-ene and (1Z,5Z)-cyclooc- H Antarafacial
ta-1,5-diene. Due to steric factor, it can not assume H C CH3
neither boat-like nor chair-like transition state. It is H [1,3]-shift
believed that reaction takes place through a diradi- H
This is not possible
cal formation. The course of the reaction is shown because geometry
here. does not permit.

PSOC_Chapter 13.indd 373 8/14/2014 2:55:20 PM


5
H2 1 4

374 Problems and Solutions in Organic Chemistry C


O H 3
2
Me
13.57 Give the product or products of each of the follow- (Contd)
ing reactions with the necessary explanations in each case. 1,5-H shift ∆
2
(a) O H2 2 3
Me ∆ C 1
+ O ? O 3 O 1
Me Me Me
O Claisen rearrangement
[3,3]-sigmatropic
(b) H2 ∆
C ? H
O
Me Aromatization
CH2
O
(c) Ph CH2
∆ OH Me
+ ?
Me
Ph CO2Me
In this case, the first step is thermal [1,5]-hydrogen shift.

l
ia
(d) O This is followed by Claisen rearrangement which is [3,3]-sig-
matropic rearrangement.

er

?
Ph

at
(c)
(e) CO2Me Ph

M

+ 50˚C Conrotory
? Ph ring opening

CO2Me
ed Ph
Ph
ht
Me
Ans Diels–Alder
ig

+
yr

(a) O CO2Me CO2Me


Me Ph Me
op

+ O
Me
The first step of the reaction is conrotatory electrocyclic
-C

O
∆ ring opening. This is followed by [4s + 2s] cycloaddition reac-
tion, commonly known as Diels–Alder reaction.
Me Me Me Me
w

O (d)
O
ie

1 O
2
O 1
O + O
ev

2 ∆
3
3 H + H
O O [3,3]-sigmatropic
Pr

O
endo-adduct exo-adduct
(Major compound) (Minor compound) OH
OH
It is case of (4s + 2s)-electrocyclic reaction, commonly
called Diels–Alder reaction. Both endo- and exo-adducts are
formed, but endo-adduct is the major product because the (Z)-2-(3-Methylpent- (E)-2-(3-Methylpent-
transition state is more stable because of secondary overlap of 2-enyl)phenol 2-enyl)phenol
orbitals of cyclopentadiene system and orbital of the carbonyl
In this case, Claisen rearrangement takes place. The
group of the malecic anhydride.
side chain formed in this process can have (E)- and
5 (Z)-stereochemistry.
(b) H2 1 4
C (e) CO2Me
O H 3
CO2Me
2
Me
50°C
1,5-H shift ∆ +
2 Cyclopropene
H2 2 3 CO2Me
1
(Contd) CO2Me
C
O 3 O 1
Me Me
Claisen rearrangement
[3,3]-sigmatropic

PSOC_Chapter 13.indd 374


H 8/14/2014 2:55:25 PM
Pericyclic Reactions 375

It is a case of Diels–Alder reaction which is [4s + 2s]-electr- 3 2


H
1
ocyclic reaction. Cyclopropene is active as dienophile because D
of its strain within the molecule. D
H
13.58 Give an example of fluxional molecule and com- (Numbering is to show
ment on its relation with pericyclic reaction. the position of the H-shift,
not IUPAC numberring)
Ans There are unsaturated polycyclic compounds which
continuously undergo very rapid sigmatropic rearrangemens [1,3] hydrogen shift
at room temperature. They are called fluxional molecules.
Bullvalene is one such molecule, first preapared in 1963 H (H)D D(H)
D Repeatedl [1,3]
by Gerhard Schrodwer. The structure was first proposed by shift (H)D D(H
Willium von E. Doering. It undergoes very rapid [3,3] sigma- D
H (H)D D(H)
tropic rearrangements giving identical forms of the molecule.
The structure of bullvalene and its rapid simatropic rearrange- (H)D D(H
ment is shown here.
On the other hand, if [1,5] hydrogen shift is considered,

l
ia
3 then only four positions are found to be enriched with deute-
2
1 rium. This is shown here.

er
1 3
2
Bullvalene 3 2
H

at
1
4 D
[3,3] sigmatropic 5 D

M
H
3 2 + (Numbering is to show
1
[3,3] sigmatropic
etc ed
the position of H-shift,
not IUPAC numbering)
ht
3 1
2 [1,5] hydrogen shift
ig

It is interesting to note that if we could labelled the each H H


Repeatedl [1,5]
yr

carbon atom individually, there would be 1,209,600 equiva- D shift (H)D D(H)
D
lent structures of bullvalene. NMR studies has revealed that
op

H H (H)D D(H)
each one of the bullvalene structures is converted into another
one at a rate of about 2000 times per second at room temper- H H
-C

ature and we always get an average structure in the laboratory


time frame. It should be noted that only two positions of the parent
compound have been labelled with deuterium and although
w

13.59 Show by isotope labeling experiment that in the positions of the deuterium have scrambled in the products,
the following compound undergoes rearrangement by the total number of deuterium atoms remains two.
ie

[1,5]-hydrogen shift rather than [1,3] hydrogen shift. The experimental result was that even when the reaction is
ev

carried out for a long times, deuterium appeared only in the


positions predicted by [1,5] hydrogen shift. Therefore, rear-
Pr

rangement occurs through [1,5] hydrogen shift.

Ans The compound shown above undergoes rearrangement 13.60 Identify the type of shift in the following transfor-
to give cyclooctatriene compound. This rearrangement could mation and discuss its stereochemical aspect.
be through [1,3] hydrogen shift or [1,5] hydrogen shift. This
is shown here. CH3 CH3
H ∆
3 2
H H H
1 ∆ T D
H [1,3] hydrogen shift H T D

3 2
1 H ∆
4 H Ans It is case of [1,7] sigmatropic rearrangement hydrogen
H [1,5] hydrogen shift
5
H shift. It involves 8 electrons (4n system) and thermal reaction
involves antarafacial. Therefore, the hydrogen shift gives a
If a deuterium labelled compound, as shown as follows, is chiral centre where the position of the hydrogen is above the
taken, then [1,3] shift of deuterium can also occur and deuterium π-electron plane of the product molecule. The course of the
can become scrambled to all the positions of the compound. reaction is given here.

PSOC_Chapter 13.indd 375 8/14/2014 2:55:30 PM


200° C
* *CH2 CH2
H2C CH2
H H
(A) (B)
376 Problems and Solutions in Organic Chemistry
O3 O3
Zn, H2O Zn, H2O
CH3 CH3 (Contd)
∆ S-configuration HC = O HC = O
* *
1 H CH3CH = O + HCH = O + + CH3CH = O
T D
2 7 T D HC = O HC = O
H
3 6 +
4 5 HCH = O
[1,7]-Antatrfacial
sigmatropic * *
hydrogen shift Isolation of HCH = O, CH3CH = O, HCH = O and CH3CH = O
* *
HCH = O, CH3CH = O, HCH = O and CH3CH = O confirms that the reaction mixture contains
13.61 (a) How can you prove that the following reaction two types of molecules differing in the position of the
involves a [1,5] hydrogen shift? labelled carbon. Thermal [1,5] hydrogen shift can account
200° C for the experimental results.
(b) According to selection rules, thermal [1,3] suprafacial
H2C CH2 CH2 CH2
single atom migration occurs through inversion of config-
H H uration at the centre of migration. The following reaction

l
(b) Give an example to show that suprafacial [1,3] sigma- results confirm this prediction.

ia
tropic migration of carbon occurs with inversion of

er
configuration.
Ans

at
(a) Reaction shown above is a case of [1,5] suprafacial sig- H3C H
1

M
matropic hydrogen shift. This is shown here. Not IUPAC 2
3 numbering 3
2
1
H2C CH2
4 200° C
CH2 CH2 ed [1,3] Sigmatropic
ht
5
H shift
H
(A) (B)
ig

150° C
The compounds (A) and (B) are homomeric, therefore,
yr

some experimental methods are to be used to ascertain


H3C H H CH3 H
op

that interconversions of (A) to (B) are [1,5] sigmatropic CH3


hydrogen shift. This can be done by using 14C (*) labelled
+
-C

compound, followed by ozonolysis. This is shown here.


200° C Inversion
* *CH2 CH2 H3C (95%)
w

H2C CH2 H (6S)-6-Methylbicyclo


H H [3.1.0]hex-2-ene
ie

(A) (B)
ev

O3 O3 Retention
Zn, H2O Zn, H2O (5%)
Pr

(6R)-6-Methylbicyclo
HC = O HC = O (Contd) [3.1.0]hex-2-ene
* *
CH3CH = O + HCH = O + + CH3CH = O
HC = O HC = O
+ EXERCISES
HCH = O
13.1 What is meant by the term ‘pericyclic reactions’? (b) H
Give examples of (a) Cycloaddition, (b) Electrocyclic, hν Heat
? ?
(c) Sigmatropic, and (d) Ene reactions.
H
13.2 On the basis of Woodward–Hoffmann selection rules,
identify the compound formed in each of the following
reactions.
(c) Me
(a) Cl Cl H hν
Heat ?
? Me
H H H

PSOC_Chapter 13.indd 376 8/14/2014 2:55:35 PM


Pericyclic Reactions 377

(d) Heat (b)


H ?
+ ?
CHO
H

13.3 What do you mean by ground state electrocyclic reac- (c)


COOCH3
tion and excited state electrocyclic reaction? Discuss the + ?
Frontier molecular orbital (FMO) method of predicting via-
bility of electrocyclic reactions.
(d) OCH3
13.4 What would be the configuration of the product/prod-
ucts in each of the following electrocyclic reactions? + ?
COOCH3
(a) cis-3,4-Dimethylcyclobutene Thermal ring closure ?
Photochemical ring closure
(b) cis-3,4-Dimethylcyclobutene ? (e) O
H
Thermal ring closure Ph
(c) (2E,4Z,-6E)-Octa2,4,6-triene ?

l
+ O ?

ia
Thermal ring closure Ph
(d) (2E, 4E)-Hexa2,4-diene ? H

er
O
Photochemical ring closure
(e) (2E,4Z,6E)-Octa-2,4,6-triene ? (f) COOC2H5

at
13.5 Give examples of (4n + 2) and (4n) π-electrons cycload- COOCH3 + ?

M
dition reactions. Which of them is supra–antara and which is
supra–supra in allowed reaction? COOC2H5

13.6 What do you mean by the order [i,j] of a sigmatropic ed


13.11 The following compound undergoes rearrangement
ht
rearrangement? Give examples. Define cheletropic reactions when heated to 200o C to an isomeric compound. Give its
with example. IUPAC name mentioning the stereochemistry.
ig

13.7 Give examples of [1,5] and [3,3]-sigmatropic rearrange- H


yr

ments and discuss their mechanism and stereochemistry.


op

13.8 Show with example that all-suprafacial sigmatropic


reactions are possible thermally when (4n + 2) electrons are H
-C

involved, where n = 1, 2, 3, etc.


13.9 An all-suprafacial [3,3]-sigmatropic rearrangements 13.12 The following unsaturated lactone gives cyclobu-
could in principle occur either through a chair-like or a boat- ta-1,3-diene and carbon dioxide on irradiation. Show the reac-
w

like transition state. Which of these two transition states is tion and explain.
ie

preferred in the following sigmatropic rearrangement? O


ev

(a) H R
R H O
Pr

180° R
H
R 13.13 What product or products are formed when the follow-
H H
H ing compound is heated? Identify the major product.

H CH3 H
(b)
R H
180° C R
R
R H H
13.14 The heating of 3-deuterioindene causes scrambling
13.10 Identify the product with stereochemistry in the fol- of the label to all three non-aromatic positions. Explain this
lowing Diels–Alder reactions. observation.
(a) O
H D
+ O Heat
? D
O D

PSOC_Chapter 13.indd 377 8/14/2014 2:55:42 PM


378 Problems and Solutions in Organic Chemistry

13.15 What happens in the following reactions? (b) Optically active compound ‘A’ racemizes on heating
(a) Me at 50oC with a half life of 24 hours. Rationalize this
∆ observations.
H

Me H
Active compound
H
(b) Me (A)

?
13.18 (a) When heated, the compound ‘A’ in presence of
Me (E)-butene-2-diaote ‘B’ gives the compound ‘C’. Explain the
(c) ∆ reaction.
?
CO2CH3
O CO2CH3
Me + 180° C

l
(d) Me H3CO2C 'B''

ia
'A' CO2CH3
?
Me Me

er
13.19 Explain the following reactions and comment on the
13.16 Rationalize the following reaction by FMO and explain pathway.

at
the steps involved. (a) R
R

M
(a) Ph hν H
Ph CO2Me R1
+
CO2Me

edR
1 H
ht
Ph (b)
Ph ∆ hν
+ H H
ig

(b) Me

yr

Me
13.20 Give the mechanism of the following reaction with
explanation.
op

13.17 (a) Predict the product with explanation: Me


-C

O O
(i) O O
* ∆ Me Me O ∆ H
CH2 ? + O
Me O H
= Me
w

* 14C Me O
ie

(ii) Et O

?
ev

Me
Pr

(iii) A

?

PSOC_Chapter 13.indd 378 8/14/2014 2:55:48 PM