Pericyclic Reactions
By
Bapu R. Thorat
M.Sc. SET. NET. MS-CIT
Assit. Professor
Dept of Chemistry & Dept of Biotechnology,
Government of Maharashtra,
Ismail Yusuf College of Arts, Science and Commerce,
Jogeshwari (East), Mumbai - 60
Chemical Reactions
Pericyclic
Reaction
Addition
Elimination
Substitution
Rearrangement
Oxidation
Reduction
Thermal and Photochemical
Electrolysis
Pericyclic Reactions
Free radical
intermediate
Chemical reaction
Mechanism
Charged
intermediate
(Ionic intermediates
such as cation, anion,
zwitter ion, etc)
Transition State
formation
1. Proceeds in single transition state.
2. Reactions not influenced by any solvent, reagent, structural changes, catalysts, etc.
3. These are highly stereospecific in nature.
4. These reactions are initiated either by heat or light but not by reagent or catalyst.
Such class of reactions are called as pericyclic reactions.
Reactions are either carried out thermally or photochemically.
The chemical reaction in which starting material is converted into a single stereo-isomeric
product is called as stereospecific or regiospecific reaction.
Pericyclic Reactions
Pericyclic Reactions
Thermal Reactions
Activated by heat
Photochemical Reactions
Activated by radiation energy
The chemistry of activated molecule in thermal and photochemical reactions is totally
different. Hence, different products are obtained for the same reaction under different
reaction conditions such as photochemical and thermal processes
hv
Ketonic Sensitizer
Cis-
Trans-
Pericyclic Reactions
Pericyclic reactions (pericyclic means shifting of electrons around the circle) are first
explained by the scientist Hoffman and Woodward in 1965.
Pericyclic reactions are highly stereospecific, proceeds through cyclic transition state
(proceed by the simultaneous reorganization of bonding electron pairs by way of cyclic
transition states). The most useful observation of these reactions is the product obtained
during this reactions having different stereochemistry than the reactant.
Electrocyclic
reactionsRing closer and ring
opening
Sigmatropic
rearrangement
Pericyclic
reactions
Cycloaddition
reactions
Ene reactions
Pericyclic Reactions
Electrocyclic reactions-
Process in
which n bonds convert into (n-1) & one
bond and vice versa.
Ring closer-
Ring openingIf the substitutions are
present on the rotating
carbons also rotate in
same direction
Two atomic (molecular) orbitals forming
a -bond may be rotating in opposite
directions, one in clockwise and other in
anticlockwise manner is called as disrotatory process
dis ratatory
Two atomic (molecular) orbitals forming a
-bond may be rotating in same direction
either in clockwise or anticlockwise manner
is called as con-rotatory process.
con rotatory
Molecular orbital symmetry
Bonding molecular
orbitals having
lower energy &
contains electrons
in G.S.
Molecular orbitals
1. Mirror plane symmetry (m): A and C
Antibonding
molecular orbitals
having higher
energy & are
empty at G.S.
2. (C2) axis of symmetry: B and D
CH2
B
A
(Bonding MO)
H2C
CH2
H2C
buta-1,3-diene
C
(Antibonding MO)
1. Mirror plane symmetry (m) is a plane
passing through the center of the molecular
orbital and perpendicular to the molecular
orbital axis, it bisect the molecular orbital in
two parts, one part is mirror image of other
part. It is maintained by Dis rotatory
process.
2. (C2) axis of symmetry is assume to
present if the rotation of the molecular
orbital around the axis by 1800 (360/2)
gives raise to another orbital, then
reflect it across a plane perpendicular
to the axis. It is maintain by con rotatory
process.
Plane of symmetry
C2 axis of symmetry
Anti-Bonding pi-orbital
Bonding pi-orbital
Plane of symmetry
C2 axis of symmetry
Sigma-bond
C2
Orbitals
M
S
A
S
A
C2
A
S
S
A
Molecular orbital symmetry
1,3-butadiene, total number of molecular orbitals are 4- 1, 2, 2*, 1* where 1 and 2 are
bonding and 2*and 1* are antibonding molecular orbitals. They are also denoted as- (1,
2, 3 and 4).
Orbitals
M
C2
1
S
A
2
A
S
3
S
A
4
A
S
1,3,5-hexatriene, total number of molecular orbitals are six i.e. 1, 2, 3, 3*, 2*, 1* where
1, 2 and 3 are bonding and 3*, 2*and 1* are antibonding molecular orbitals. They are
also denoted as- (1, 2, 3, 4, 5 and 6)
Orbital
M
C2
1
S
A
2
A
S
3
S
A
4
A
S
5
S
A
6
A
S
Node
When we move in molecular orbital, the sign of the orbital change (above the plane or
consider all orbitals below the plane) is called as node.
For a linear conjugated -system the wave function n will posses (n-1) nodes.
If (n-1) is zero or even integer, n will be said to be symmetric with respect to
m and antisymmetric with respect to C2.
If (n-1) is an odd integer n will posses the C2 axis of symmetry and
antisymmetric with respect to m.
Node = 0
Node = 1
Node = 2
Node = 3
Frontier Molecular Orbital [FMO] Method
Molecular orbital model for analyzing pericyclic reactions has been proposed by Kenichi
Fukui of Japan.
The correlation diagram is useful for the detail analysis of an Electrocyclic reactions.
Mirror (m) of symmetry
CH2
H2C
Z
D
Antibonding MO
Y
C
C2 axis of symmetry
X
B
Bonding MO
W
A
Frontier Molecular Orbital [FMO] Method
A similar conclusion is obtained by considering the symmetry of highest occupied molecular
orbital [HOMO] of open chain partner in Electrocyclic reactions.
Mirror (m) of symmetry
CH2
H2C
Z
D
Antibonding MO
Y
C
C2 axis of symmetry
X
Thermal
HOMO
Bonding MO
W
A
Frontier Molecular Orbital [FMO] Method
A similar conclusion is obtained by considering the symmetry of highest occupied molecular
orbital [HOMO] of open chain partner in Electrocyclic reactions.
Mirror (m) of symmetry
CH2
H2C
Z
D
Antibonding MO
Photochemical
HOMO
Y
C
C2 axis of symmetry
X
B
Bonding MO
W
A
Frontier Molecular Orbital [FMO] Method
If the HOMO having C2-axis of symmetry (node is odd), then reaction will follow conrotatory path.
If it posses a mirror plane symmetry (node is zero or even number), a reaction will follows
dis-rotatory path.
In thermal process the highest occupied molecular orbital [HOMO] is the higher energy
bonding molecular orbital (B in above example).
In photochemical process one electron from higher energy bonding molecular orbital is
excited into low energy antibonding molecular orbital (C in above example) [first
excited state] therefore first excited state containing electron is HOMO (SUMO) i.e.
LUMO lowest unoccupied molecular orbital.
Thermal
Reactions
Photochemical
Reactions
Transition State
Configurational Preference
4n + 2 (aromatic)
Disrotatory
4n (antiaromatic)
Conrotatory
Transition State
Configurational Preference
4n + 2 (aromatic)
Conrotatory
4n (antiaromatic)
Disrotatory
Electrocyclic Reactions (Examples)
Me
Me
Me
dis,hv
Me
Total Electrons
T.S.
4
Antiaromatic
Symmetry
m
Me
and/or
Process
h
Me
HOMO
3
Node
2
Process allowed
Dis
dis,heat
H H
Me
and/or
H H
Me
Me
Me
Me
H
Me
Process
Total Electrons
T.S.
6
Aromatic
Symmetry
m
HOMO
3
Node
2
Process allowed
Dis
Process
hv
Total Electrons
T.S.
6
Aromatic
Symmetry
C2
HOMO
4
Node
3
Process allowed
Con
hv
3.
HH
Process
h
Me
Me
Dis rotatory
Me
Me
and/or
HH
Me
Me
Total Electrons
T.S.
8
Antiaromatic
Symmetry
m
HOMO
5
Node
4
Process allowed
Dis
Cycloaddition Reactions
It is class of pericyclic reactions in which the system having m electrons is
added into the system having n electrons forming cyclic product.
It is versatile route for the synthesis of cyclic compounds having high degree of
stereo selectivity under thermal and photochemical reaction conditions.
Depending on the number of electrons taking part in the reaction, is called as
(m+n) or (m+n+.) Cycloaddition reactions.
Or
A concerted combination of two -electron systems to form a ring of atoms
having two new bonds and two fewer bonds is called a cycloaddition reaction.
(2+2) cycloaddition
(4+2) cycloaddition
+
O
O
O
NC
CN
+
NC
(4+2) cycloaddition
(2+2+2) cycloaddition
CN
NC
NC
CN
CN
Cycloaddition Reactions
The most common cycloaddition reaction is the [4+2] cyclization known as the
Diels-Alder reaction in which cyclic product is formed from alkene and a diene.
The four -electron system is called as diene and the two -electron system is
called as dienophile.
The stereochemistry of the substituent attached to double bonded carbon atom
is maintained.
The diene containing electron donating group while dienophile containing
electron withdrawing groups are easily undergo (4+2) cycloaddition reaction.
(4+2) cycloaddition
O
(2+2+2) cycloaddition
NC
NC
two step mechanism
CN
one step mechanism
CN
zwitterions
.
or
diradicals
NC
NC
CN
CN
Cycloaddition Reactions
OAc
COOCH3
OAc
COOCH3
In each case the diene reactant is colored blue, and the new -bonds in the
adduct are colored red. The stereo specificity of these reactions should be
evident.
In the first example, the acetoxy substituents on the diene have identical Econfigurations, and they remain cis to each other in the cyclic adduct.
Likewise, the ester substituents on the dienophile have a trans-configuration
which is maintained in the adduct.
The reactants in the second equation are both monocyclic, so the cycloaddition
adduct has three rings. The orientation of the quinone six - membered ring with
respect to the bicycloheptane system (colored blue) is endo, which means it is
oriented cis to the longest or more unsaturated bridge. This can be explain
by Cis-Principle.
The alternative configuration is called exo.
Cycloaddition Reactions
In cycloaddition reactions, addition of two systems having double bonds takeplace either in same or opposite side of the system. Such mode of addition is very
important to decide the stereo chemistry of product. These different numbers of
modes are named as suprafacial (on the same side) and antrafacial (on the
opposite side).
This specification is usually carried out by keeping a suitable subscript (s or a) after
the number referring to the pi-components. E.g. The Diels-Alder reaction is also
called as (4s+2s) cycloaddition.
[antrafacial]
[suprafcial]
R
+
R
heat
(4s+2s)
R
Frontier Molecular Orbital [FMO] Method
[Cycloaddition Reactions]
There is an alternative approach to determine whether or not a cycloaddition reaction is
allowed which can be found to depends on the symmetry properties of the highest occupied
molecular orbital (HOMO) of one reactant and the lowest unoccupied molecular orbital
(LUMO) of other molecule. The favorable interaction can be predicted from the sign of
HOMO and LUMO.
e.g. During Cycloaddition of ethylene to cyclobutane (2s+2s) addition is thermally forbidden
because lopes of HOMO of one ethylene molecule and that of other LUMO of another
ethylene molecule are not having corresponding similar signs, it (2a+2s) thermally allowed.
But when one ethylene molecule is irradiated, on electron get excited to excited state
(antibonding molecular orbital) which is now become HOMO which is then correlated to
LUMO of other unexcited ethylene molecule. Therefore, it is photochemically (2s+2s)
allowed.
HOMO
HOMO of excited state.
(2s + 2s)
LUMO of unexcited state.
LUMO
(Ground state)
[ , forbidden]
(Excited state)
[ hv, allowed]
Frontier Molecular Orbital [FMO] Method
[Cycloaddition Reactions]
In Diels-Alder reaction as sign of the 1,4lopes of butadiene HOMO have been
found to be matching those in the LUMO
of ethylene. The (4s+2s) addition is
thermally allowed and photochemically
forbidden whereas (4a+2s) or (4s+2a) is
photochemically allowed and thermally
forbidden.
The
Diels-Alder
reaction
of
cyclpentadiene
to
forming
dicyclopentadiene. Invariably, the endodimer is formed rather that exo-dimer
because of favorable secondary force due
to interaction of frontier orbitals of diene
and dienophile compounds which leads to
lower the energy of the transition. In figactual bonding have been connected by
full lines and the secondary interactions
shown by broken lines.
(4s + 2s,
(4s + 2s,
, allowed)
, allowed)
(4s + 2a or 4a + 2s, hv , allowed)
HOMO
+
(endo form)
LUMO
HOMO
(exo form)
LUMO
Dipolar Cycloaddition Reactions
Dipolar cycloaddition reactions take place between unsaturated hetero atom compounds, such as
diazoalkanes, alkyl and aryl azides, nitrile oxides and nitrones, and alkene or alkyne functions.
Although the former reactants are neutral, their Lewis structures have formal charges, and may be
written as 1,3-dipoles. The alkene and alkyne functions to which the dipoles add are called
dipolarophiles.
Two have adjacent or 1,2-charge separation, and two have the 1,3-dipolar charge separation noted
above. The 1,2-dipolar structures retain valence shell octets for all heavy atoms, suffer less charge
separation, and have one more bond than do the 1,3-dipolar structures. Therefore, the most
representative Lewis structures for these compounds are 1,2-dipoles, not 1,3-dipoles.
Sigmatropic Rearrangement
Many thermal and photochemical rearrangements are known which involve the
shifting of a -bond flanked by one or more -electron systems to a new
position [i,j] with in the molecule. It is an uncatalyzed intramolecular process.
This rearrangement involve shifting of the -bond, hence called as sigmatropic
rearrangement of the order [i,j]. The i and j are two number set in the square
bracket and the numbering of system is done by starting with atoms from
which the migration of the -bond started.
In some rearrangements, the migrating -bonds lie between two conjugated
bond systems. e.g. Cope & Claisen rearrangements.
e.g. 1.
R1
2'
[1,3] shift
R1
2.
R1
[1,5] shift
R1
3'
(3,3) shift
1'
1
X
2
(X - C<, O)
3
Sigmatropic Rearrangement
Suprafacial and Antrafacial processes
In sigmatropic rearrangement, the -bond migrates across the -bonds through the
two different stereo-chemical sources.
Migrated -bond gets moved across the same face of the conjugated system,
suprafacial process
migrating -bond get reformed on the opposite -electron face of the
conjugated system, antrafacial process i.e. migrating group migrate at opposite
face of the conjugated system.
e.g. [1,5] sigmatropic shift shows both these stereo-chemical consequences as-
H
B
antrafacial
H
B
C
B
C
suprafacial
B
H
Because of these reasons, suprafacial migrations are more common than the
antrafacial shift. As lengthing of the migrating system increases, antrafacial shift
also increases. The antrafacial [1,3] shift is thermally impossible.
FMO Methods (Sigmatropic Rearrangement)
The analysis of the sigmatropic rearrangement shows that the migrating bond gets
cleaved homolytically resulting pair of radicals. The migrating group get migrates
over the HOMOs of the conjugated system. e.g. Analysis of suprafacial [1,5]
sigmatropic shift of hydrogen in which the homolytic cleavage gives rise to the
production of hydrogen atom and pentadienly radical.
Homolytic
..
cleavage
Bond
formation
The ground state electronic configuration of pentadienly radical is 122231 and
HOMO is 31 of this radical possess same sign on the terminal lopes (plane
symmetry). Therefore thermally [1,5] migration is suprafacially allowed.
H
H
H
H
3
FMO Methods (Sigmatropic Rearrangement)
The first excited state electronic configuration of pentadienly radical is 122241
and HOMO is 41 of this radical possess opposite sign on the terminal lopes (C2
axis of symmetry). Therefore photochemically [1,5] migration is antrafacially
allowed.
122231 4050
122230 4150
Ground state
Excited state
A similar analysis shows that, for the system [i,j] possess i+j = 4n+2 electrons, the
thermal reaction should be suprafacial and photochemical process should be
antrafacial but for those cases i+j = 4n, the thermal reaction should be antrafacial
and photochemical process should be suprafacial. These rules are summarized as
followi+j
-allowed
h-allowed
4n
antrafacial
suprafacial
4n+2
suprafacial
antrafacial
FMO Methods
Electrocyclic reaction
No. of electrons No. of nodes
involved
Type of transition -allowed
state
4n
Zero or even
Antiaromatic
4n
Odd
Aromatic
Con
4n+2
Zero or even
Aromatic
Dis
4n+2
Odd
Antiaromatic
h-allowed
Dis
Con
Cycloaddition addition
No. of electrons No. of nodes
involved
Type of transition -allowed
state
4n
Zero or even
Antiaromatic
4n
Odd
Aromatic
4n+2
Zero or even
Aromatic
4n+2
Odd
Antiaromatic
Supra-antra
Antra-supra
Supra-supra
Antra-antra
-
h-allowed
Supra-supra
Antra-antra
Supra-antra
Antra-supra
Sigmatropic rearrangement
No. of electrons No. of nodes
involved
Type
of -allowed
transition state
4n
Zero or even
Antiaromatic
4n
Odd
4n+2
4n+2
h-allowed
supra
Aromatic
Antra
Zero or even
Aromatic
supra
Odd
Antiaromatic
antra
Ene Reaction
The joining of a double or triple bond to an alkene reactant having transferable
allylic hydrogen is called an ene reaction.
The allylic hydrogen undergoes 1,5-migration with change in the position of the
allylic double bond.
Like Diels Alder reaction, it is also 6 electron electrocyclic reaction, but here
two sigma-electrons of the allylic C-H -bond takes the place of two -electrons of
the diene in Diels Alder reaction.
+
Y
H
H
X=Y -
C=C, C=O, C=S, N=O, N=N, etc.
Cope Rearrangement
The 1,5-dienes isomerizes {[3,3] rearrangement} on heating up to 3000C. Reaction
is normally reversible and gives mixture of starting material and product. The
position of equilibrium is depends on the stability of the starting material and the
products. The temperature needed for the reaction is depends on the substituents
and relative strain of the double bonds of 1,5-system. If the substituent R is
attached to double bonded carbon then energy of the transition state is lowered and
reaction occurs at 165 1850C.
O
2'
1'
3'
3'
[3,3] rearrangement
HO
1'
2'
3'
[3,3] rearrangement
1'
[3,3] rearrangement
2'
150 0 C,
100%
1hr
3'
OH
[3,3] rearrangement
5.
90%
320 0 C
6.
[3,3] rearrangement
OH
H+
4.
[3,3] rearrangement
2'
1'
KH, THF, reflux 18 hrs.
98%
H
O
HO
Cope Rearrangement
A common example of Cope rearrangement involving [3,3] sigmatropic
rearrangement in 1,5-diene (meso-3,4-dimethyl-1,5-hexadiene) on heating
(pyrolysis) giving exclusively cis,trans-isomer of 2,6-octadiene. This reaction
proceeds through six membered six electron transition state.
CH3
CH3
H3C
meso-3,4dimethyl-1,5hexadiene
CH3
CH3
CH3
CH3
H3C
Z,E-2,6-octadiene
Bu-n
Bu-n
H3C
CH3
KH, THF, RT
18-crown-6
HO
H3C
H3C
O
CH3
CH3
H3C
CH3
OHC
CH3
CH3
CH3
HO
Bu-n
15 C
KH, THF, RT
18-crown-6
H3C
O
CH3
CH3
H3C
OHC
CH3
CH3
CH3
Claisen Rearrangement
The Claisen rearrangement provides an excellent stereoselective route for the
synthesis of ,-unsaturated carbonyl compounds from allylic alcohols through
allyl vinyl ethers. This reaction involves [3,3]-sigmatropic rearrangement and
takes place through a cyclic six membered transition state. The importance of
this reaction is the formation of carbon-carbon bond due to expense of carbonoxygen bond. It is highly stereoselective leading predominantly E-configuration of
the new double bond. The cyclic transition state preferred chair conformation with
the substituent R1 in the less hindered pseudoequatorial position.
R1
Heat
O
R2
R1
R1
O
R2
O
R2
(R2 = H, alkyl, OR, OSiR3, NR2)
The aromatic Claisen rearrangement involves [3,3] sigmatropic rearrangement of allyl
aryl ethers with migration of the allyl group (with allylic transposition) to the ortho position
of the aromatic ring. If ortho-position of the ring is substituted then double rearrangement is
occur and gives para-substituted product instead of ortho-substitution.
O
O
OMe
190 C
decalin
Br
CH3
OH
OMe
OMe
Br
Br
CH3
CH3
Examples
1. The concerted photochemical reaction between two olefins
leading to a cyclobutane ring isa. 2s + 2a cycloaddition. b. 2s + 2s cycloaddition.
c. 2s + 2s cycloaddition. d. 2s + 2a cycloaddition.
LUMO
HOMO
supra-supra
LUMO
HOMO
antra-antra
LUMO
HOMO
supra-supra
LUMO
HOMO
antra-antra
It is example (2+2) cycloaddition reaction. It is photochemical process,
therefore consider first excited state (LUMO) of first olefine is HOMO which is
then correlated to LUMO of second olefine (unexcited form). Therefore answer
is (b).
Examples
2. The intermediate A and the major product B in the following
conversion areCOOH
NaNO2/HCl
NH2
1. A is carbocation and B is
2. A is carbanion and B is
NH2
3. A is free radical and B is
4. A is benzyne and B is
It is combination of two reactions- Benzyne formation and Diels Alder reaction. The
anthranilic acid undergoes diazotizing followed by decarboxylation forming benzyne. It
shows [4+2] cycloaddition reaction [Diels Alder reaction] forming cyclic product (4).
NaNO2
HNO2
ClH
NaCl
O
COOH
+
COOH
HNO2
NH2
N2 Cl
O
N2 Cl
[4+2] cycloaddition rea.
Diel's Alder reaction
B
Examples
3. The structures of the major products X and Y in the following
transformation areO
1.
O
3.
2.
Y=
X=
X=
Y=
O
O
Y=
X=
hv
Y=
4. X =
O
During Diels Alder reaction between cyclic diene and substituted dienophile
forming endo product rather than exo because of favorable secondary force due to
interaction of frontier orbitals of diene and dienophile compounds which leads to lower
the energy of the transition (3). The X further undergoes photochemical [2+2]
cycloaddition reaction of alkene and carbonyl group (Paterno-Buchi reaction) forming
oxetane [four membered cyclic ether].
Examples
4. Suggest the mechanism of following reaction.
O
O
1,5-carbon
Ans:
1,5-hydrogen
sigmatropic shift
sigmatropic shift
1,5-sigmatropic Carbon shift
1,5-sigmatropic Hydrogen shift
HOMO
HOMO
Process
Total Electrons
6
HOMO
3
Node
2
T.S.
Aromatic
Process allowed
Suprafacial
Examples
5. Suggest the mechanism of following reaction.
hv
Step I is [2+2] cycloaddition reaction forming cyclobutane. It is [2s + 2s] process.
LUMO
LUMO
H
hv
H
A
HOMO
antra-antra
HOMO
supra-supra
node 2, antiaromatic transition state, suprafacial allowed
Step II is [3+3] sigmatropic rearrangement reaction called Cope rearrangement proceeds through
six membered cyclic (chair form) transition state.
H
A
H
Cyclic chair form six membered
transition state
Example
6. Suggest the mechanism of following reaction.
MeOOC
COOMe
COOMe
O
+
?
COOMe
Step I
HOMO
COOMe
LUMO
COOMe
Total electrons - 6, node- 2,
Aromatic T.S., Supra-supra
process allowed
O
O
or
Step II
COOMe
COOMe
CO2
It is electrocyclic ring opening
reaction.
COOMe
MeOOC
COOMe
Step III.
or
COOMe
+
COOMe
COOMe
It is [4+2] cycloaddition reaction
called Diel's Alder reaction. The
substituent on dienophile is endo
when using cyclic diene.
Examples
7. Suggest the mechanism of following reaction.
D
It is electrocyclic ring opening reaction.
D
D
Process
Thermal
Total ele
4
HOMO
2
Node
1
Symmetry
C2
Process allowed
Con
D
D
Examples
8. In the following concerted reaction, the product is formed by a-.
H
1.
2.
3.
4.
6-pi disrotatory electrocyclisation
4-pi disrotatory electrocyclisation
6-pi conrotatory electrocyclisation
4-pi conrotatory electrocyclisation
The triene skeleton of cyclo octatetraene undergoes electrocyclic ring closer
reaction. The total number of electrons takes part in the reaction are 6,
therefore HOMO of the reaction is 3. The node of reaction is 02, therefore m
plane of symmetry is maintained. The m (plane of symmetry) has been
maintained by dis-rotation.
Process
Thermal
Total electrons
6
HOMO
3
Node
2
Symmetry
m
Process allowed
Dis
Process
Thermal
Total electrons
4
HOMO
2
Node
1
Symmetry
C2
Process allowed
Con
H
con rotation
H
H
dis rotation
H
Examples
9. The product formed and the process involved in the following
reaction is OK
OK
[3,3] sigmatropic rearrangement
1.
O
[1,3] sigmatropic rearrangement
2.
O
[5,5] sigmatropic rearrangement
3.
O
4.
[1,5] sigmatropic rearrangement
The selection rule for sigmatropic rearrangement is
The total number of electron involved for the sigma-tropic rearrangement is
(4n +2) electron, then it is thermally suprafacial and photochemically
antrafacial through the aromatic transition state.
OK
2
3
1
2
CH2
CH2
CH2
CH2
4
OK
OK
CH2
OK
CH2
CH2
CH2
OK
CH2
CH2
[3,3] sigmatropic rearrangement
CH2
CH2
[5,5] sigmatropic rearrangement
Explain the following reaction -
H2C
H2C
RT
H3C
H2C
H2C
OCH 3
0 C
97%
+
+
CH2
CH2
H3CO
CH2
CH2
H
O
CH2
CH3
100 C
and
H
H
0 C
0%
0 C
37%
CH2
H2C
CH3
H3C
CH3
CH3
NO 2
80 C
CH2
Bu3SnH
H 3C
PhMe, AIBN
H 3C
H 3C
CH 3
Explain the following reaction -
H2C
H2C
RT
H3C
H2C
H2C
CH3
100 C
and
OCH 3
H3CO
H
O
The dienophile containing electron withdrawing group and diene containing electron
donor are undergoes Diels Alder reaction. Along with steric effect, electronic effect
can also plays important role.
O
O
H2C
CH
RT
CH
H2C
CH 2
H3CO
O
CH3
CH3
CH 2
100 C
O
CH2 H3C
CH 2
CH2
OCH 3
O
H3CO
H
O
CH3
O
C
CH 2
H3CO
H
O
H
O
Explain the following reaction -
0 C
97%
+
CH2
CH2
CH2
CH2
CH2
H
H
0 C
0%
0 C
37%
CH2
The isolated double bond and diene do not usually take part in intermolecular
Diels Alder reactions, but number of cyclic alkenes ( and alkynes) with
considerable angle strain are reactive dienophiles or dienes. The drawing
force for these reactions is though to be the reduction in angle strain
associated with the transition state for the addition.
Explain the following reaction CH3
H2C
NO 2
H3C
CH3
H 3C
Bu3SnH
80 C
PhMe, AIBN
CH2
H 3C
H 3C
CH3
CH 3
But energy difference between LUMO of dienophile and HOMO of diene is relatively
higher and interaction between them is poor therefore carried out at higher T.
Substituents (bulky substituents) such as methyl group on the diene discourage the diene
from adopting the cisoid conformation and hence hindered the reaction.
-
H2C
CH3
Steric
repulsion
H
H3C
H
H2C
CH3
CH3
Total nine structures possible in which -CH2 carbon of
terminal methylene group having negative charge while
only three structures are possible in which carbon of
-CMe 2 group having negative charge
CH3
CH3
CH3
H3C
CH3
H3C
CH3
H3C
CH3
CH3
NO 2
N
O
Electron rich carbon
H2C
CH2
NO 2
CH2
Electron deficient center
CH3
H3C
Bu3SnH
80 C
H3C
NO 2
H3C
CH3
+
CH2
CH2
H3C
H3C
NO 2
PhMe, AIBN
H3C
H3C
CH3
H3C
H3C
CH3
Examples
CH3
CH3
a.
i. LDA
iii. H O +
ii.
b.
Et
O
c.
O
i. Et3 N
Cl
H3 C
H
H3 C
O
Cl
d.
ii. PhCH=NPh
Cl
e.
f.
O
g. H3C
CH3
CH3
+
O
MeO
O
h.
CH3
CH3
i.
hv
j.
?
CO2Me
CO2Me
CH3
CH3
3
1
LDA
a.
O
CH3
CH2
H2C
O
CH3
acid
H2C
H3O+
HO
CH3
This reaction involves [3,3]-sigmatropic rearrangement and takes place
through a cyclic six membered transition state. The importance of this reaction
is the formation of carbon-carbon bond due to expense of carbon-oxygen bond.
CH2.
O
CH.
CH3
CH2.
CH3
CH3
CH3
Con rotation
b.
Et
CH3
Et
CH3
CH3
c.
CH3
CH3
Con rotation
CH3
CH3
d . If proceeds through formation of Carbene which shows (2+2) cycloaddition with imine
forming cyclic amide.
OH
H3C
CH3
e.
f.
*
CH2
H3C
CH3
H3C
CH3
H3C
CH3
H3C
CH3
g.
Photochemistry and Pericyclic reactions
Predict the product and its stereochemistry for the following reactions.
Indicate for each reaction
(i) Type of pericyclic reaction. (ii) Necessary selection rule.
5.
CH3
hv
i.
ii.
CH3
NC
iii.
CN
?
+
NC
CN
CH3
3.
i.
CH3
hv
O
?
ii.
200 0
?
(alkali soluble)
COOCH3
iii.
+
COOCH3
