Chapter 15 Conjugated Systems

The good thing about Ch 15 is that there are very few new reactions: you really only need to know the 1,2/1,4
addition, and the Diels Alder reaction. However, you must know these reactions in detail! It is important
to know EVERYTHING about Diels Alder reaction: reaction, mechanism, stereochemistry, Regiochemistry, etc. Diels
Alder reaction is the Meat of this chapter, so know it very well!
Reactions of conjugated dienes
Reaction
1,2 and
1,4
addition
to
conjuga
ted
dienes

Example (Mechanism)
A conjugated diene can extract a hydrogen (from HBr, H+
and H2O, etc), forming a carbocation intermediate. Notice
that the carbocation forms adjacent to a double bond
because of resonance, stabilizing the carbocation. If
the reaction takes place in cold conditions, or the absence of
heat, then the bromine will directly attack the initial
carbocation formed, forming the 1,2 product, also
known as the kinetic product

If this reaction takes place under heated conditions, then this

allows the carbocation to switch places and rearrange onto
the first carbon. Notice that this resonance structure is
less stable than the secondary carbocation. This process
requires extra energy that is provided by heat. Bromine can
then attack the primary carbocation, forming the 1,4
product, also known as the thermodynamic product.
The thermodynamic product is the more stable
product, but the kinetic product provides for a more
stable intermediate. This is very important, and know
the difference between the two!

Reactants, Reagent,
Products
Reactant- A diene
Reagent An
electrophile (An
electrophile that can
provide a proton
source, following a
nucleophilic attack,
can be HCl, HBr, H+
and H2O)
Product Alkene
with a nucleophile
attached either at
1,2 position, or 1,4
position

Stereochemistry
and
Regiochemistry
Regiochemistry
Either 1,2 or 1,4
addition
1,2 Is
kinetically
favored (more
stable
carbocation/tran
sition state, but
less stable
product, formed
at lower
temperature)
1,4 Is
thermodynamica
lly favored (less
stable
intermediate,
but more
stable/substitute
d product,
formed at higher
temperatures)

Important things to
note
-Know this
reaction
mechanism and
the properties of
it! Especially know
the difference
between the
kinetic and
thermodynamic
product
-Remember,
Kinetic = more
stable
intermediate
Thermodynamic
more stable
product
-Whenever they give
you heat, they are
wanting the
thermodynamic
product. If they do
not, they are
wanting the kinetic
product

Formati
on of
Allylic
radical
(Chapte
r 4)

-Remember from ch 4, a halogen gas can react with light,

producing two halide radicals
A bromine radical can then extract a hydrogen from the allylic
carbon, allowing for resonance with the double bond. The
bromine can then attack on either side (You dont need to
worry about kinetic vs. thermodynamic products for this
reaction)

-Another way of forming bromine radicals is to react with NBS

(shown below on the bottom left. NBS allows constant
regeneration of the bromine radical (it will act like reacting
with Br2 and hv)

Reactant- A
conjugated system
(multiple double
bonds adjacent to
each other)
Reagent Br2 and
light, or NBS
Product Allylic
bromide, with the
bromide placed on
the most stable
radical.

N/A

-Dont need to
know the
mechanism, but
know the general
reaction just in
case
Remember:
-Stability of Radical
Resonance 1st, then
3o, 2o, 1o
-The radical is placed
on the carbon that is
with resonance with
the double bond
-NBS is used to
regenerate HBr back
to Br2, which is used
to create 2 Br
radicals

SN2
reaction
of an
allylic
compou
nd
(Ch 6)

-An allylic compound, such as an allylic alkyl halide, can

undergo a SN2 reaction, resulting in a substitution reaction of
the nucleophile and the leaving group. The difference
between normal SN2 reactions with ordinary alkyl halides
versus allylic alkyl halides is that the transition state of
the allylic alkyl halide is stabilized by the conjugation
of the double bond

Reactant- A
conjugated system
(multiple double
bonds adjacent to
each other)
Reagent Any SN2
Nucleophile
Product SN2
product, depends on
the nucleophile
attacking

Stereochemistry Inversion of
configuration
Remember that
SN2 reactions
involve an
inversion of
configuration (just
switch the
substitutent
stereochemistry
from wedge to
dash)

You should
already know the
general
mechanism by
now. The main
thing that the
transition state of
the SN2 reaction
is stabilized by
the double bond

Diels-Alder Reaction
General Reaction
The Diels-Alder reaction is the addition of a diene (2 alkenes adjacent to each other)
with a dienophile (general term for something reactive towards a diene, usually a single
alkene or alkyne). This reaction involves the transfer of electrons from 2 pi
bonds to form two sigma bonds, creating a new ring structure, usually a
cyclohexane with a double bond, or a cyclohexene. Depending on the substituents
attached or the structure of the dienophile, this can form more complex products. To
draw the arrows for the movement of electrons, the easiest way I usually draw
it is to draw the diene on the left side, and the dienophile on the right side.
The pi bond electrons are simply moving counter-clockwise. The double bond
from the dienophile is shifted left to create a sigma bond with the top carbon of the
diene, the top diene pi bond is shifted down to form a double bond on middle carbons
(C2 and C3), and the bottom pi bond is shifted to the right to make a sigma bond with
the bottom carbon of the dienophile. Below I have shown the proper way to draw the
flow of electrons in a Diels Alder reaction, and the product that forms.

Properties
There are some important properties that you should know about Diels-Alder Reactions.
The Diels-Alder Reaction involves the interaction of the HOMO (Highest
occupied molecular orbital) of the diene with the LUMO (lowest
unoccupied molecular orbital) of the dienophile. In order for the two sigma
bonds to form between the diene and dienophile, they must get close enough to
interact with each other. The rate of reaction depends on the energy gap
between the HOMO of the diene and the LUMO of the dienophile. The
smaller the energy gap, the greater the interaction between the orbital and the
more reactive the species are towards Diels-Alder. Therefore, to lower the
transition state between the two orbitals and increase the rate of the
reaction, we must increase the energy of the HOMO and decrease the
energy of the LUMO. To do that, we can place substituents that have electron
withdrawing/donating effects
o Electron donating groups increase the amount of energy in a
molecular orbital, so it is usually placed on the dienophile. Examples
of electron donating groups are listed below. Know these! It will be
useful in later chapters!

Ex: -CH3, -OH, -OCH3, -NH3, amides

Electron withdrawing groups decrease the amount of energy in a
molecular orbital, so it is usually placed on the diene. Examples of
electron withdrawing groups are listed below. Know these! It will be
useful in later chapters!
Ex: Halogens, Aldehydes, Carboxylic acids, Esters, -CN, -NO 2
Stereochemistry of Diels Alder Reaction
Basic Stereochemistry

The stereochemistry of this reaction is very important! Lets take an example and
go through the mechanism, including the stereochemistry. Below I have shown an
example of butadiene and an alkene with a cyanide attached. The orbitals of each one
are shown below as well. During a Diels-Alder reaction, the HOMO orbitals of the diene
are interacting with the LUMO orbitals of the dienophile. To help stabilize the
transition state, the electron withdrawing group placed on the dienophile is
preferentially placed UNDER the diene. This helps to stabilize the formation of the pi
bond that is forming. Below is the proper orientation of the diene and dienophile, and the
location of the electron withdrawing group

Now imaging flipping up the new sigma bonds that have been created so that the entire
cyclohexene is planar. The cyanide is now pointing down as a consequence of being
initially placed under the diene. This position is called the endo position, and is
the preferred stereochemistry of the Diels Alder reaction, known as the endo
rule. This is usually shown on the product as a dash.

If the electron withdrawing group was not placed below the diene, but instead outside of
it, then the resulting product would have the cyanide pointing up. This is known as the
exo position, and is the minor product of a Diels-Alder reaction. This is not
preferred! You want to TRY to put ALL of the substituents in the ENDO
position!

Below I have shown the endo and exo positions of the possible substituent that was
attached to the dienophile. In general, endo positions are pointed DOWN, and exo
positions are pointed UP.

Another important aspect about the stereochemistry of the Diels Alder is that the diene
must be placed in the s-cis configuration. If it is not initially placed in the s-cis, you
must rotate the diene to make it s-cis, if possible! Otherwise, a Diels-Alder reaction
will not occur! (Note that the s-cis configuration is different from a cis configuration on
an alkene, because we are talking about the orientation of the two double bonds to
each other, NOT the substituents that are attached to the double bond)

Stereochemistry of substituents attached to the Dienophile

So we know that the substituents on the dienophile prefer to be placed in an endo
position, but what about multiple substituents? In a Diels Alder reaction, the
dienophile must react with the diene in a syn-addition. Therefore, substituents
that are placed cis to each other on the dienophile will allow both of them to
be placed in the endo position, shown below.

Substituents that are placed trans to each other only allow for one substituent
to be placed in the endo position. The other one must be placed in the exo
position. This is shown below

Stereochemistry of substituents attached to the Diene

The stereochemistry of the substituents attached on the Diene is also important. This is
determined by the initial stereochemistry of the substituent on the diene. If the
substituent is placed trans (not s-trans) on the carbon 1 and 4 of the diene, then
the resulting product will have the substituent be pointing down and away
from the page, or a dash.

If the substituent is placed cis on the 1 or 4 position of the diene, this will result in
sterics interfering with the orbitals interacting with each other. This will then result
with the substituent pointing up and towards the page. This is shown as a
wedge. Note that substituents placed on the 2 and 3 position remain in the
page, and are still a single line.

To sum up the stereochemistry of a Diels Alder reaction

The diene must be placed in a s-cis configuration. If it is not initially, but
can be rotated to a s-cis configuration, do it!
The substituents on the dienophile react in a syn-addition, and prefer to
place the substituents in the endo position, which helps stabilize the
transition state, again shown as a dash. If there are two substituents placed
in cis, they can both go endo. If there are two substituents in trans, one
goes in the endo, one goes in the exo
Substituents on the diene are more straightforward. Trans substituents
are dash, and cis substituents are wedge. Substituents on 2 and 3 dont
matter
Regiochemistry
The regiochemistry is also very important for this reaction, but is pretty easy to figure
out.
To find the Regiochemistry of the product, place arbitrary charges on each of the
main carbons relative to its electron density. Start with the carbon with the
substituent, and place an arbitrary charge on it (+ if there are electron
withdrawing groups attached, or if there are electron donating groups
attached). Once you placed a charge, alternate the charges as you move to
another carbon (if the first carbon you marked was +, the carbons adjacent to it
would be -, and so on). Do this for both the diene and the dienophile. Afterwards,
match the opposite charges of the diene with the dienophile to
determine the regiochemistry (This is the method that Dr. Biewer goes over in
his website). Notice that the substituents are usually placed in a 1,4 position
or a 1,2 position, but rarely 1,3 to each other (When in doubt, place the
substituents 1,2 or 1,4 to each other)