Escolar Documentos
Profissional Documentos
Cultura Documentos
l
ia
13.1 What is meant by ‘pericyclic reaction’? Give classifi- Ene reactions:
er
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
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.
w
[m + n]
+
unoccupied. In such a case, the occupied molecular orbital is
ev
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.
l
ia
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
yr
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
(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
electrons activation
with the stereo cyclobutene-1-ene give the same stereochemical outcomes.
op
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
w
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
Me H
H H Suprafacial
way of bond formation
l
ia
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
w
Me Me
H H (2Z., 4Z)-hexa-2,4-diene
ie
Me Me
ev
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.
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-
l
ia
phile and this mode of addition leads to the formation of an
er
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
yr
+ 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
Me Me
CN CN
ev
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
w
H3O+
both are supra-supra cycloadditions leading to the formation
ie
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
.
+
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
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
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
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
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
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
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
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
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
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
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
CO2Me lowers the energy of the LUMO of the alkene part. That is
why the second reaction occurs at a faster rate.
ev
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
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
O reactions.
op
CO2H O CO2H
-C
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)
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
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
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
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 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
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.
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
Me H
H
H
w
Me H
ie
ev
(a) 2 2
Heat 3 3
?
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
+ 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
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
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
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
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
hν
[1,5]-shift
ev
H Me CH3
Pr
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
(i) H
H2C H3C 300°C
CH3 CH3
OH O Cl C
S H2
O 350°C
H H2 H
[1,5]-shift C
+
+ SO2
Cl C
H2 H H
(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
H2 H
Ans
C (a) It is a case of [3,3]-sigmatropic rearrangement involv-
CH2 350°C
w
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
+ 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
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
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
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
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)
trans-1,2-Divinylcyclobutane
H H ∆
(II)
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
(c)
∆ (s-cis conformation)
?
-C
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
+ 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
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
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
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
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.
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
(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
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
like transition state. Which of these two transition states is tion and explain.
ie
(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
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
O O
(i) O O
* ∆ Me Me O ∆ H
CH2 ? + O
Me O H
= Me
w
* 14C Me O
ie
(ii) Et O
hν
?
ev
Me
Pr
(iii) A
∆
?