Chapter 13

1. Introduction
❖ A conjugated system involves at least
one atom with a p orbital adjacent to
at least one p bond

conjugated allylic allylic allylic

diene radical cation anion
O

enone enyne
2. Allyl Radical
❖ A conjugated system increase stability

Can look at it two ways:

1. Molecular orbital diagram
2. Resonance structures
2a. Molecular Orbital Diagram of the
Allyl Radical
2b. Resonance Description of the
Allyl Radical

2 2
1 3 1 3

3
3
2 2
1
1
2c. Radical Stability

Copyright © 2016 by John Wiley & Sons, Inc. All rights reserved.
2d. Halogenation of the Allylic Position

Chapter 10
Copyright © 2016 by John Wiley & Sons, Inc. All rights reserved.
3. The Allyl Cation
❖ Relative order of carbocation stability
5. Alkadienes & Polyunsaturated
Hydrocarbons
❖ Alkadienes (“Dienes”)
2 4
1
3 2 3
1,3-Butadiene
1 4

2 4 6 6 5
1 1,3-Cyclohexadiene
3 5
(2E,4E)-2,4-Hexadiene
❖ Alkatrienes (“Trienes”)
2 4 6 8

1 3 5 7

(2E,4E,6E)-Octa-2,4,6-triene
❖ Alkadiynes (“Diynes”)

❖ Alkenynes (“Enynes”)
6 5 6 7
4 1 3 5 8

2 2 4
3

Hex-1-en-5-yne (2E)-Oct-2-en-6-yne
❖ Conjugated dienes

❖ Isolated alkenes
❖ Cumulenes
Enantiomers?

H H H H
C C C C C C
H H H H
(Allene)
(a 1,2-diene)
6. 1,3-Butadiene: Electron
Delocalization
6A. Bond Lengths of 1,3-Butadiene
1.47 Å
2 4

1 3

1.34 Å
sp3 sp sp3
sp2 sp3

1.54 Å 1.50 Å 1.46 Å

6B. Conformations of 1,3-Butadiene
trans
single single
bond bond

cis
(s-cis) (s-trans)

H H

(less stable)
6C. π-Molecular Orbitals of 1,3-Butadiene

Double bond
character!
7. The Stability of Conjugated
Dienes
❖ Conjugated alkadienes are thermo-
dynamically more stable than isomeric
isolated alkadienes
H o (kJmol-1)

2 + 2 H2 2 2 x (-127)=-254

+ 2 H2 =-239

Difference 15
8. Ultraviolet–Visible Spectroscopy

❖ The absorption of UV–Vis radiation is

caused by transfer of energy from the
radiation beam to electrons that can be
excited to higher energy orbitals
8A. The Electromagnetic Spectrum
monoenes
8C. Absorption Maxima for Noncon-
jugated and Conjugated Dienes

More Conjugated
lower Energy Gap
9. Electrophilic Attack on Conju-gated
Dienes: 1,2 and 1,4-Addition
2 4
H Cl
1 3 25oC

Cl
H + H
Cl
(78%) (22%)
(1,2-Addition) (1,4-Addition)
 H
❖ Mechanism
X
Cl H + H
(a)
Cl
H
(a)
(a) + +

Cl
H H
(b) (b)
(b)
H
Cl
9A. Kinetic Control versus
Thermodynamic Control of a
Chemical Reaction
Br
-80oC
+
Br
(80%) (20%)
+
HBr Br
+
40oC Br
(20%) (80%)
 Br o
40 C, HBr

Br
1,2-Addition 1,4-Addition
product product

More Stable
10. The Diels–Alder Reaction:
A 1,4-Cycloaddition Reaction
of Dienes
[4p+2p]
+

(diene) (dienophile) (adduct)

Nobel Prize in Chemistry in 1950

Otto Diels Kurt Alder

❖ e.g.
O O

benzene
+ O O
100oC

O O
1,3-Butadiene Maleic Adduct
(diene) anhydride (100%)
(dienophile)

Concerted Mechanism
10A. Factors Favoring the Diels–Alder
Reaction
Type A EDG EDG
EWG EWG
+

Type B EWG EWG

+
EDG EDG

● Type A and Type B are normal Diels-Alder

reactions
Type C EWG EWG
EDG EDG
+

Type D EDG EDG

+
EWG EWG

● Type C and Type D are Inverse Demand

Diels-Alder reactions
❖ Relative rate
O

30oC
Diene + O D.A. cycloadduct

O
OMe

Diene > >

t1/2 20 min. 70 min. 4 h.
❖ Relative rate

20oC
+ Dienophile D.A. cycloadduct

NC CN CN CN
Dienophile > >
NC CN CN
t1/2 0.002 sec. 20 min. 28 h.
❖ Steric effects

Dienophile: > >

COOEt COOEt COOEt

Relative rate: 1 0.14 0.007

10B. Stereochemistry of the Diels–
Alder Reaction
10B. Stereochemistry of the Diels–
Alder Reaction
1. The Diels–Alder reaction is stereospecific:
the reaction is a syn addition, and the
configuration of the dienophile is retained
in the product
2. The diene, of necessity, reacts in the
s-cis rather than in the s-trans
conformation

s-cis Configuration s-trans Configuration

O O

+
R X R

Highly strained
❖ e.g.

COOMe
heat
+ No Reaction

(diene locked
in s-trans
conformation)
❖ Cyclic dienes in which the double bonds are
held in the s-cis conformation are usually
highly reactive in the Diels–Alder reaction
❖ Relative rates:
O

30oC
Diene + O D.A. cycloadduct

Diene > >

t1/2 11 sec. 130 sec. 4 h.
3. Alder-Endo Rule: The Diels–Alder reaction occurs
primarily in an endo, rather than an exo, fashion
when the reaction is kinetically controlled
H H

longest bridge R R is exo

H H H

R R is endo
❖ Alder-Endo Rule
● If a dienophile contains activating
groups (EWG, π) with p bonds they
will prefer an ENDO orientation in
the transition state
H
H
X
X
X X
❖ e.g.
O 
O O
+

H
H O

O
100% endo
O
4. Stereospecific reaction

(i) X X
+
X X

X X
+
X X
4. Stereospecific reaction
10C. How To Predict the Products of
a Diels–Alder Reaction