Third Year

Organic Chemistry Course

CHM3A2

Frontier Molecular Orbitals

and
Pericyclic Reactions

- Prof Jon A Preece -

School of Chemistry
University of Birmingham
 Prof Preece’s Powerpoint Lecture Presentations

and answers to questions can be found at…

www.nanochem.bham.ac.uk
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Course Synopsis
Part Contents

1 Pericyclic Reactions These lectures will begin with a definition of Pericyclic reactions, and will be
exemplified by considering examples of cycloaddation, sigmatropic, and electrocyclic reactions. It will be
highlighted how it is possible to use FMO theory (and other theories) to predict the constitution and
stereochemical outcome of the products. Attention will be drawn to the cyclic transition state and the number of
electrons involved (Huckel or Mobius), highlighting that when 4n+2 electrons are involved the reaction proceeds
readily under thermal conditions, and the reversibility of such reactions. The concept of Linear Combination of
Atomic Orbitals to form a bond(s) (and antibond(s)) will be revised, and extended to the linear combination of
frontier molecular orbitals. The p-molecular orbitals of ethene, butadiene and 1,3,5-hexatriene will be considered
and the identities of the HOMO and LUMO will be established, as well as the FMOs of a C–H bond.

2i Electrocyclic Reactions This lecture will extend the predicative nature of FMO theory regarding the
stereochemical outcomes to electrocyclic reactions for 4 and 6 p-electron transition states (by defining the
disrotatory or conrotatory movement of the termini of the HOMO in the Transition State).

2ii Cycloaddition Reactions These lectures will introduce cycloaddition reactions and the concepts of (i) phase
relationships of the FMOs, (ii) geometry of approach of the FMOs (suprafacial and antarafacial will be
defined), and (iii) minimum energy differences between the HOMO and LUMO. These concepts will be
exemplified by several Diels-Alder and related reactions. Attention will be drawn to the nature (chemical and
stereochemistry) of substituents and their stereochemistry in the product.

3 Photochemically Induced Pericyclic reactions These lecture will extend the predicative nature of FMO
theory regarding the outcomes of electrocyclic reactions and cycloaddition reactions by considering how they can
be induced photochemically, to give alternative stereochemical outcomes and allow reactions that did not go
thermally.
Part 1. Frontier Molecular Orbitals

Constructing molecular orbitals and identifying the frontier

molecular orbitals

Part 2. Thermal Pericyclic Reactions

(i) Electrocyclic Reactions using FMO Theory

(ii) Cycloaddition Reactions using FMO Theory

Part 3. Photochemical Pericyclic Reactions

(i) Electrocyclic Reactions using FMO Theory

(ii) Cycloaddition Reactions using FMO Theory

 Second Year Organic Chemistry Course
CHM3A2

Recommended Reading

I Fleming
Frontier Orbitals and Organic Chemical Reactions, John Wiley and Sons, 1996.

Part 1: Ch 1 and Ch 2
Part 2 and 3: Ch 4
 Second Year Organic Chemistry Course
CHM3A2
Frontier Molecular Orbitals and
Pericyclic Reactions

Part 1(i):

The Questions FMO Analysis Can

Answer

100% 0%
Ionic And Radical Reactions
To date you have seen two broad categories of reaction:

(i) Ionic reactions

Here pairs of electrons move in one direction

e.g. SN2, SN1, E2 and E1 mechnisms

B
H R23 BH R1 R2
R
R1R4 Cl R4 R3 Cl

(ii) Radical reactions

Here single electrons move in a correlated manner

e.g. chlorination of alkanes

CH3 Cl Cl H3C Cl Cl
Pericyclic Reactions

Pericyclic reactions are the third distinct class.

They involve cyclic transition states

In which all bond breaking and bond making steps take place in

commensurate manner

And there is no sense of the flow of electrons.

Pericyclic Reactions: Electrocyclic Reactions

Stereospecific Reaction

Clockwise
100% 0%

There is no real senses of flow for

the electrons in pericyclic reactions
Anti-Clockwise
Pericyclic Reactions: Cycloaddition Reactions

Stereospecific Reaction Kinetic Thermodynamic

Product Product

CO2Me  CO2Me CO2Me

CO2Me CO2Me
CO2Me

100% 0%
Regiospecific Reaction

MeO
MeO CHO
 MeO CHO

CHO

0% 100%
Revision: 1,3–Syndiaxial Interactions

Br
1,3-syndiaxial interactions

H
Br
H Br
H H
H
H H
Br H
H 1
H
3
2
axial H

H
Br H
H
H
Br Br H
H H
H
H
equitorial H
H
Thermodynamic and Kinetic Control

Kinetic Thermodynamic
Product Product
Formed in Not Formed in
Cycloaddition MeO C CO2Me Cycloaddition
2 MeO 2C CO2Me
Reaction Reaction

H H

CO2Me H

CO2Me CO2Me

CO2Me
H H
MeO2C H
MeO2C MeO 2C

H MeO 2C
H H
Pericyclic Reactions: Sigmatropic Reactions

Stereospecific Regiospecific
Reaction Reaction
H
D D
Me
Me
Me
H
D

100% 0%
Pericyclic Reactions: Why are they so specific?

Pericyclic reactions show high degrees of

(i) Stereoselectivity

(ii) Regioselectivity, and

(iii) Diastereoselectivity

Thus, an obvious question to ask ourselves at this point is why are

pericyclic reactions so selective?

To help begin to answer this question we shall briefly need to revise the
SN2 reaction mechanism where YOU WILL remember that this reaction
type was highly stereoselective leading to inversion of chiral centres.
Revision: SN2 Reaction Mechanism

Bimolecular
R1 Process Nucleophile attacks from behind
Nu Cl the C-Cl s-bond.
3
R Rate = k[R-Hal][Nu]
R2
This is where the s*-antibonding
sp3
Rate
Determinig orbital of the C-Cl bond is
Step situated.

1 R1 1 R1
– –
2 2
Nu Cl Nu Cl
R3

R3 R2
R2
Inversion
Bond Bond of Configuration
Forming Breaking

Transition State –
Energy Maxima

sp2
The concerted flow of both pairs of electrons in the SN2 reaction
mechanism leads to the transition state which allows the
stereochemical information to be retained,

i.e. a stereoselective reaction.

This SN2 reaction mechanism should be contrasted to the SN1 reaction

mechanism where the arrow-pushing is the same but the two pairs
electrons do not flow in a concerted fashion. Instead, the haloalkane
C-Cl bond heterolytically cleaves to give the planar sp2 hybridised
carbocation reactive intermediate. Now the nucleophile can attack
from either side of the carbocation leading to racemisation,

i.e. a non-stereoselective reaction.

Revision: Transition States
Discussion of reaction mechanisms frequently include discussions of the
nature of the transition state for each step in a reaction sequence – or at least
for the slowest or rate limiting step.

A transition state is the point of highest energy in a reaction or in each step of

a reaction involving more than one step.

The nature of the transition state will determine whether the reaction is a
difficult one, requiring a high activation enthalpy (G‡), or an easy one.

Transition states are always energy maxima, I.e. at the top of the energy hill,
and therefore, can never be isolated: there are no barriers to prevent them
from immediately “rolling” downhill to form the reaction products or
intermediates (or even reform the starting materials).

A transition states structure is difficult to identify accurately. It involves partial

bond cleavage and partial bond formation. However, it is nigh on impossible to
estimate whether the transition state is an early one (looks more like the
starting materials) or a late one (looks more like the products)
Revision: Transition States

Transition
State

Energy
Maxima

E
n
e G‡
r
g Starting
y A+B
Material

Go
Product
C+D

Reaction Coordinate
Pericyclic Reactions: Transition States

Thus, now we can start to understand why pericyclic reactions are so

highly stereo-, regio-, and diasteroselective.

Pericyclic reactions involve concerted flow of pairs of electrons going

through transition states which retains stereochemical information that
was present in the starting material.
Pericyclic Reactions Involve Cyclic Transition States

CO2Me

CO2Me

CO2Me
CO2Me Cyclic
Transition
CO2Me
CO2Me State

CO2Me

CO2Me
Pericyclic reactions involve ene and polyene units.
CO2Me
Thus, the transition states involve the overlap of p-
molecular orbitals in the case of electrocyclic and CO2Me
cycloaddition reactions, and a p-molecular orbital
and s-molecular orbital in the case of sigmatropic
reactions.

How do the orbitals overlap?

CO2Me

CO2Me
Frontier Molecular Orbitals

In order to understand the selectivity of pericyclic reactions, we need to

understand these molecular orbitals and how they overlap.

In particular, we need to know how the Frontier Molecular Orbitals

(FMOs) interact in the starting material(s) which lead to the cyclic
transition states.

We will first revise some simple molecular orbitals of a C-H s-bond and
a C=C p-bond and then extend this analysis to highly conjugated linear
polyenes and related structures/
 Second Year Organic Chemistry Course
CHM2C3B
Frontier Molecular Orbitals and
Pericyclic Reactions

Part 1(ii):

Frontier Molecular Orbitals

Electronic
Ground State
4 3 nodes

Thermal
Reactions 3 2 nodes
LUMO

HOMO 2 1 node

1 0 nodes
 CHM2C3B – Learning Objectives Part 1 –
– Introduction to FMOs –

Frontier Molecular Orbitals

After completing PART 1 of this course you should have an understanding of, and be able to demonstrate, the following terms, ideas and

methods.

(i) Given a set of n p-orbitals you should be able to construct a molecular orbital energy level diagram which

results from their combination.

(ii) In this diagram you should be able to identify for each MO

nodes

the symmetric (S) or antisymmetric (A) nature of the MO towards a C2

axis or mirror plane

the bonding, nonbonding or antibonding nature of it

(iii) For a set of n molecular orbitals you should be able to identify the frontier molecular orbitals.

the highest occupied molecular orbital (HOMO )

the lowest unoccupied molecular orbital (LUMO)

(iv) The HOMO (thermal reaction) interactions are important when evaluating the probability of an
unimolecular reaction occurring and the stereochemical outcome – see electrocyclic reactions.

The HOMO/LUMO (thermal reaction) interactions of the reacting species are important when
evaluating the probability of (i) a bimolecular reaction occurring and the stereochemical
outcome– see cycloaddition reactions, and (ii) a unimolecular reaction occurring and the
stereochemical outcome – see sigmatropic reactions.

The geometry, phase relationship and energy of interacting HOMOs and LUMOS is important for
evaluating the probability of a reaction occurring and the stereochemical outcome.
s-Bond
Two s Atomic Orbitals
Molecular Orbitals

Nodal Plane
ANTI-BONDING
MOLECULAR
ORBITAL

E
N
s*
E
s ATOMIC ORBITAL
R
G
+
Y

BONDING
MOLECULAR
ORBITAL
s
s-Bond
One s Atomic Orbital and One sp3 Atomic Orbital

Molecular Orbitals

ANTI-BONDING
MOLECULAR
ORBITAL
E
N s*
E
R
sp3 ATOMIC ORBITAL
G
Y
+

BONDING
MOLECULAR
ORBITAL
s
p-Bond:
Two p Atomic Orbitals Molecular Orbitals
Nodal Plane

ANTI-BONDING
MOLECULAR
ORBITAL

E p*
N
E p-atomic orbitals
R +
G
Y

BONDING
MOLECULAR
ORBITAL

p
The linear combination of

n atomic orbitals

leads to the formation of

n molecular orbitals
A SIMPLE Mathematical Description of a MO

The combination of two (or more) p-atomic orbitals (or any orbitals) to
afford 2 p-molecular orbitals can be described by the following simple
mathematical relationship

p* = ccf1 + cdf2

p = caf1 + cbf2

fm = Electronic distribution in the atomic orbitals

Cn = Coeffecient: a measure of the contribution which the

atomic orbital is making to the molecular orbital
The probability of finding an electron in an occupied molecular orbital is 1.

The probability of finding an electron in an occupied molecular orbital is the Sc2

Thus, for the ethene p-molecular orbitals…

p* = ccf1 + cdf2 Sc2 = cc2 + cd2 = 1

1 2
Cc = 1/√2

p* Cd = -1/√2 Negative

p = caf1 + cbf2 Sc2 = ca2 + cb2 = 1

1 2
Ca = 1/√2

Cb = 1/√2
p
So what about the combination of 3 or 4
or 5 or 6 p-atomic orbitals.

That is to consider conjugated

systems…
The Allyl Cation, Radical and Anion – 3p AOs to give 3p MOs

Cl Cl H

Polar
Solvent
B

Cl Cl BH
Allyl Cation Allyl Radical Allyl Anion
Thus, allyl systems result from the combination of 3 conjugated p-orbitals.
Therefore, this will result in 3 p-molecular orbitals.

When we constructed the p-molecular orbitals of ethene, each

contributing AO was the same size, i.e. the coeffecient c were 1/√2 or -
1/√2.

When there are three or more p-atomic orbitals combining the size of each
contributing p-atomic orbital will not be equal (but they will be
symmetrical about the centre).

Finally, we refer to the p-MOs and p*-MOs as 1, 2, 3 (…n)

The Allyl p-Molecular Orbitals

We can consider the molecular orbital (the electron density) being described
by a SINE WAVE starting and finishing one bond length beyond the
molecule…

3 = 2 Nodes
Nodal + + + 3
position
4/3 = 1.33 1.33
Nodes

_ _ 2 = 1 Nodes Nodal
+ + position + + + 2
4/2 = 2 2

1 = 0 Nodes Nodal
position + + + 1
1 2 3 4
4/1 = 4
4
For our analysis of molecular orbitals we do not have to
concern ourselves with the coefficients.

We can draw the p-AOs that make up the p-MOs all the
same size.

However, we have to always remember they are not the

same size.

But it is of the utmost importance that we know how to

calculate where the nodes are placed
Bonding, Non-Bonding, and Anti-bonding Levels
Energy

3
Anti-bonding
Anti-bonding Level 2

Non-bonding
Non-bonding Level 2

Bonding Level 1
Bonding
1

We can consider the molecular orbital (the electron density) being described
by a sine wave starting and finishing one bond length beyond the molecule…
LUMOs and HOMOs

LUMO = Lowest Unoccupied Molecular Orbital

HOMO = Highest Occupied Molecular Orbital

Allyl Allyl Allyl

Cation Radical Anion
(2e) (3e) (4e)

3 LUMO LUMO
2 nodes

2 1 node LUMO HOMO HOMO

1 0 nodes HOMO
Question 1: 4 p-Molecular Orbital System – Butadiene
Construct the p-molecular orbitals of butadiene.
Identify the number of nodes, nodal positions, HOMO and LUMO.

n Number of Nodal
Nodes Position
Answer 1: 4 p-Molecular Orbital System – Butadiene
Construct the p-molecular orbitals of butadiene.
Identify the number of nodes, nodal positions, HOMO and LUMO.

n Number of Nodal
Nodes Position
4 3 + + + +
5/4 = 1.25

3 2 + + + + LUMO
5/3 = 1.66

2 1 + + + + HOMO

5/2 = 2.5

1 0 + + + +
5/1 = 5
1 2 3 4 5
A Reminder: Sinusodal Wave Function
SIMPLE MORE COMPLEX

4 3 nodes 5/4

1.25

3 2 nodes 5/3

1.66

2 1 node 5/2

2.5

1 2 3 4 5
1 0 nodes 5/1

5
Coefficients, cn

Each molecular orbital is described by an equation…

n= caf1 + cbf2 + ccf3 + cnfn

Where c is referred to as the coefficient

Such that the…

Sc2 = 1

That is to say the probability of finding an electron in a molecular orbital is 1

 3= caf1 + cbf2 + ccf3 + cdf4

3

1.66
We Keep FMO Analysis Simple!!

For the purpose of this course and the third year course (Applied Frontier
Molecular Orbitals and Stereoelectronic Effects) you are expected

(i) to be able to place the nodal planes in the correct place

(ii) but not to be able to assign the coefficients to the molecular

orbitals.

That is to say you can draw the p-orbitals that make up each
molecular orbital as the same size, whilst remembering that
in reality they are not and for high level FMO analysis this
needs to be taken into account.
Question 2: 5 p-Molecular Orbital System – Pentadienyl
Construct the p-molecular orbitals of the cyclopentenyl system.
Identify the number of nodes and nodal positions.

n Number of Nodal Molecular

Nodes Position Orbitals
Answer 2: 5 p-Molecular Orbital System – Pentadienyl
Construct the p-molecular orbitals of the cyclopentenyl system.
Identify the number of nodes and nodal positions.
Molecular
n Number of Nodal
Orbitals
Nodes Position
5 4 6/5 = 1.2 + + + + +

4 3 6/4 = 1.5 + + + + +

3 2 6/3 = 2 + + + + +

2 1 6/2 = 3 + + + + +

1 0 6/1 = 6 + + + + +
1 2 3 4 5 6
Question 3: Pentadienyl Cation, Radical & Anion
Introduce the electrons and identify the HOMOs and LUMOs
Pentenyl Pentenyl Pentenyl
cation radical anion

5 4 nodes

4 3 nodes

3 2 nodes

2 1 node

1 0 nodes
Answer 3: Pentadienyl Cation, Radical & Anion
Introduce the electrons and identify the HOMOs and LUMOs

Pentenyl Pentenyl Pentenyl

cation (4e) radical (5e) anion (6e)

5 4 nodes

4 3 nodes LUMO LUMO

3 2 nodes LUMO HOMO HOMO

2 1 node HOMO

1 0 nodes
Question 4: Pentadienyl Cation & Anion
Generate the cation and anion and draw the resonance structures of the above species

Cl H
Answer 4: Pentadienyl Cation, Radical & Anion
Generate the cation and anion and draw the resonance structures of the above species

Cl H

B:
6 p-Molecular Orbital System – 1, 3, 5-Hexatriene

6 5 nodes

5 4 nodes

4 3 nodes LUMO

3 2 nodes HOMO

2 1 node

1 0 nodes
 7 p-Molecular Orbital System cation (6e) radical (7e) anion (8e)

Nodal Plane
Position
7 6 nodes 8/7 = 1.14

6 5 nodes 8/6 = 1.33

5 LUMO LUMO
4 nodes 8/5 = 1.6

4 3 nodes 8/4 = 2 LUMO HOMO HOMO

3 HOMO
2 nodes 8/3 = 2.67

2 1 node 8/2 = 4

1 0 nodes 8/1 = 8
Question 5: 6p MO System
Ele ctro ns m o r C2
Node s m C2
By shading the p atomic orbitals,
generate the molecular orbitals for
6
hexa-1,3,5-triene .

Identify the number of nodes

characterising each molecular 5

orbital.

With reference to both a mirror 4

plane (m) and a two-fold axis,
designate the orbitals as symmetric
(S) or antisymmetric (A).
3

Using arrows to represent electrons,

associate the six p-electrons with
the appropriate molecular orbitals
2
of hexa-1,3,5-triene in its ground
state.

1
Finally, identify the HOMO and
LUMO.
Answer 5: 6p MO System
m or C2
By shading the p atomic orbitals, Nodes m C2

generate the molecular orbitals for

6 5 A S
hexa-1,3,5-triene .

Identify the number of nodes

characterising each molecular 5
4 S A
orbital.

With reference to both a mirror

4 LUMO
plane (m) and a two-fold axis, 3 A S
designate the orbitals as symmetric
(S) or antisymmetric (A).
3 HOMO
2 S A
Using arrows to represent electrons,
associate the six p-electrons with
the appropriate molecular orbitals
2 1 A S
of hexa-1,3,5-triene in its ground
state.

1
Finally, identify the HOMO and 0 S A
LUMO.
 Question 6: MO System

Protonation of A affords B. Draw the three resonance H

structures of B in which the positive charge has O O

formally been shifted from the oxygen atom onto H3O H2O
three of the five carbon atoms
.

A B

H
Considering only these three resonance O
structures, how many

(i) carbon atoms are involved in the

hybrid structure,

(ii) carbon p-orbitals are there,

(iii) p-electrons are associated with the

carbon atoms, and

(iv) molecular orbitals are associated

with the combination of these carbon p-
orbitals

In an analogous fashion to how question 1 was set out, draw out the molecular orbitals resulting from the p-orbital
combination on this carbon framework, making sure you identify all of the items listed in question 1.
 Answer 6: 5p MO System
H
Protonation of A affords B. Draw the three resonance
O O
structures of B in which the positive charge has
H3O H2O
formally been shifted from the oxygen atom onto
three of the five carbon atoms
.
A B

H
O
Considering only these three resonance
structures, how many

(i) carbon atoms are involved in the

hybrid structure,
5
(ii) carbon p-orbitals are there, 5
(iii) p-electrons are associated with the
carbon atoms, and 4 H
O
H
O
H
O
(iv) molecular orbitals are associated
with the combination of these carbon p- 5
orbitals

In an anologous fashion to how question 5 was set out, draw out the molecular orbitals resulting from the p-orbital
combination on this carbon framework, making sure you identify all of the items listed in question 5.
 O

Pentenyl
cation (4e)
Mirror Plane C2 axis

5 4 nodes S A

4 3 nodes A S

3 2 nodes LUMO S A

2 1 node A S
HOMO

1 0 nodes S A
 Second Year Organic Chemistry Course
CHM2C3B
Frontier Molecular Orbitals and
Pericyclic Reactions

Part 1(iii):

HOMO and LUMO Combination

What is the Driving Force for Controlling Pericyclic
Reactions?

The driving force which controls the product outcome in

pericyclic reactions is the in phase combination of the

FMOs (the HOMO and LUMO) of the reacting species in

the transition state.

FMO Theory is Extremely Powerful.

Pericyclic Reactions Involve Conjugated Polyene Systems

Pericyclic reactions involve conjugated polyene systems.

Enes and Polyenes are made by the linear combination of p-AOs.

Thus, we first need to construct the molecular orbitals of polyenes.

Then we need to identify the Frontier Molecular Orbitals.

Finally, we will need to construct the correct geometry for orbital

overlap of the FMOs in the transition states of the reactions.

 HOMOs and LUMOs
Highest Occupied Molecular Orbitals
Lowest Unoccupied Molecular Orbitals
In bimolecular reactions (like the SN2 and the Diels-Alder reaction), interaction
between the two molecular components is represented by interaction between
suitable molecular orbitals of each.

The extent of the interaction depends upon the geometry of approach of the
components since the relative geometry affects the amount of possible overlap.

It also depends on the phase relationship of the orbitals – and also upon their
energy of separation, a small energy favouring a greater interaction.

Generally, the two reactants will interact, via the highest occupied molecular
orbital (HOMO) of one component and the lowest unoccupied molecular orbital
(LUMO) of the other component, the so-called frontier molecular orbitals (FMOs).
Consider the next five frames to appreciate this paragraph of text. Consider an
SN2 Reaction…
 Revision: Transition State Geometries of Nucleophiles
Attacking sp3 Tetrahedral Centres

TET  Nu X
Nu X Nu X
sp3

 = 180°
Inversion of Configuration
Supports this Attack Angle

Nucleophile HOMO s* C–X

LUMO
s* C–Nu

X
Nu

sC–Nu
NucleophileHOMO
s* C–X
LUMO
The orbital containing the lone pair of electrons on the Nu
is the…

HOMO (Highest Occupied Molecular Orbital)

The s* orbital of the C-X bond is the…

LUMO (Lowest Unoccupied Molecular Orbital)

Any bimolecular reaction can be analysed in this fashion

Frontier Molecular Orbital Theory (FMOs)

This analysis of FMOs (HOMOs and LUMOs) for such a simple reactions may
seem pointless for a simple SN2 reaction.

It is not!

Understand it.

Appreciate that for a bimolecular reaction the HOMO of one component

interacts with the LUMO of the second component. (Additionally, for
unimolecular reaction the HOMO of the molecular component dictates the
reaction course).

In this course we will examine the use of FMOs to explain and predict the
outcomes of a class of reactions referred to as pericyclic.

The use of FMOs is an extremely powerful tool to the synthetic organic chemist
when analysing and predicting the outcome of pericyclic reactions.
 CHM3A2 – Summary Sheet Part 1 –
– Introduction to FMOs –

Frontier Molecular Orbitals

Molecular orbital theory is a powerful and versatile asset to the practice of organic chemistry. As a theory of bonding it
has almost superseded the valence bond theory.

Molecular orbital theory has

proven amenable to pictorial non-mathematical expression,

given the right answers to some decisive questions in organic chemistry,
proven the theory of most theoretical chemists,
given insight into not only to the theory of bonding, but also to the theory of making and breaking chemical bonds, and
proven a theory which has been able to explain the pattern of reactivity in a class of reactions, known as pericyclic
reactions.

In this course we will concentrate solely on the use of MO theory in predicting the outcome of pericyclic reactions. But it
should not be forgotten that MO theory is applicable to other types of chemical reraction

To understand the importance of MO theory, we shall consider three types of pericyclic reactions and show how frontier
molecular orbitals of the reactants can be used in a predicative nature to work out whether the reaction will proceed and
what the stereo/regiochemical outcome will be.

The three types of pericyclic reactions we will consider are

electrcyclic reactions
cycloaddition reactions
sigmatropic reactions

We will see how it is possible to predict the stereoselectivity, diastereoselectivity, and regioselectivity of pericyclic
reactions by the analysis of the FMOs of the transition states
The precise construction of the p-molecular orbitals by the linear combination of p-atomic orbitals is extremely important if
FMO theory is to yield the correct stereochemical product outcomes,

Key points to note when constructing p-molecular orbitals from the combination of p-AOs are

(i) the combination of n Aos always affords n MOs

(ii) The lowest p-MOs (1) has no nodal planes
(iii) The next highest (2) has one nodal plane, and so on
(iv) The nodal planes need to be placed exactly in the Mos as described in the lecture notes
(v) Electrons fill from the lowest MO first with no more than two electrons in each MO.