Conjugated Systems

Allylic groups

TEMA 4
Qumica Orgnica 2014

Definitions
Conjugated double bonds are separated by
one single bond. Example: 1,3-pentadiene.
Isolated double bonds are separated by two
or more single bonds. 1,4-pentadiene.
Cumulated (Alenos) double bonds are on
adjacent carbons. Example: 1,2-pentadiene.
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Resonance Energy
Heat of hydrogenation for trans-1,3pentadiene is less than expected.
H for 1-pentene is 30.0 kcal/mol and for
trans-2-pentene is 27.4 kcal/mol, so expect
57.4 kcal for trans-1,3-pentadiene.
Actual H is 53.7 kcal, so the conjugated
diene is more stable.
Difference, (57.4 53.7) 3.7 kcal/mol, is the
resonance energy.
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Relative Stabilities
twice 1-pentene
more substituted

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Structure of 1,3-Butadiene
Most stable conformation is planar.
Single bond is shorter than 1.54 .
Electrons are delocalized over molecule.

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Conformations of
1,3-Butadiene
s-trans conformer is more stable than the
s-cis by 2.3 kcal.
Easily interconvert at room temperature.
H
H
H

H
H

H
H

s-trans

H
H
s-cis H

H
H

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Allylic groups

Allylic Cations

Carbon adjacent to C=C is allylic.

Allylic cation is stabilized by resonance.
Stability of 1 allylic 2 carbocation.
Stability of 2 allylic 3 carbocation.
H

+
H2C C CH2

+
H2C

H
C CH2
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1,2- and 1,4-Addition

to Conjugated Dienes
Electrophilic addition to the double bond
produces the most stable intermediate.
For conjugated dienes, the intermediate
is a resonance stabilized allylic cation.
Nucleophile adds to either carbon 2 or 4,
both of which have the delocalized
positive charge.
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Addition of HBr
H H
H2C C C CH2

H H

H3C

C C
+

H H
CH2

H3C

_
Br

H H
H3C

C C

C C CH2
+
_
Br
H H

CH2

Br
1,2-addition product

H3C

C C

CH2

Br
1,4-addition product

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Kinetic vs.
Thermodynamic Control
Major product
at 40C

Major product
at -80C
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Allylic Radicals
Stabilized by resonance.
Radical stabilities: 1 < 2 < 3 < 1 allylic.
Substitution at the allylic position competes
with addition to double bond.
To encourage substitution, use a low
concentration of reagent with light, heat, or
peroxides to initiate free radical formation.
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Allylic Bromination
h

Br2
H

2 Br
H

Br

+ HBr
H

H
H

H
H

H
Br Br

Br Br
H
Br

H
H

Br

+ Br
=>

H
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Bromination Using NBS

N-Bromosuccinimide (NBS) provides a
low, constant concentration of Br2.
NBS reacts with the HBr by-product to
produce Br2 and prevent HBr addition.
O
N
O

O
Br + HBr

N H
O

+ Br2
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MOs for the Allylic System

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Diels-Alder Reaction
Otto Diels, Kurt Alder; Nobel prize, 1950
Produces cyclohexene ring
Diene + alkene or alkyne with
electron-withdrawing group (dienophile)
H

W
C

C
H

H
C W
C H
H

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Examples of
Diels-Alder Reactions
N

H3C

+
H3C

diene

C
C

H3C

H3C

dienophile
O

C H
H

Diels-Alder adduct
O
C OCH
3
C

C
C

C C N

OCH3

C
OCH3

C OCH
3

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Stereochemical Requirements
Diene must be in s-cis conformation.
Dienes C1 and C4 p orbitals must
overlap with dienophiles p orbitals to
form new sigma bonds.
Both sigma bonds are on same face of
the diene: syn stereochemistry.
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Concerted Mechanism

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Endo Rule
The p orbitals of the electron-withdrawing
groups on the dienophile have a secondary
overlap with the p orbitals of C2 and C3 in
the diene.

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