CHM 501
OLEFIN CHEMISTRY
DR. L.O. EKEBAFE
MODULES TO BE TREATED IN THIS SECTION
INCLUDE:
1. Concerted Reactions: Frontier Orbital treatment of
pericyclic reactions
2. Aromatic transition state treatment: Huckel/Mobius
transition states
3. Electrocyclic rearrangements and cycloadditions
4. Introduction to sigmatropic shifts
MODULE 1
CONCERTED REACTIONS
FRONTIER ORBITAL TREATMENT OF
PERICYCLIC REACTIONS
A concerted reaction is a chemical reaction in
which all bond breaking and bond making occurs
in a single step.
•NO Reactive intermediates
•NOT affected by solvent polarity, large buildup
of charge in the transition state
PERICYCLIC REACTIONS: Definition
Pericyclic Reactions are concerted reaction that
proceed via a cyclic transition state
A pericyclic reaction is a type of organic reaction
wherein
•the transition state of the molecule has a cyclic
geometry,
•the reaction progresses in a concerted fashion,
• and the bond orbitals involved in the reaction
overlap in a continuous cycle at the transition state.
Peculiar Characteristics of Pericyclic
Reactions
1. It is a concerted reaction
2. The cyclic transition state is a must
3. No distinct intermediates in the reaction
4. Bond forming and bond breaking steps are simultaneous but not
necessarily synchronous
5. Requires light or heat
6. They are stereospecific: that is. A single stereoisomer of the
reactant gives a single stereoisomer of the product
7. The symmetry of the molecular orbitals must be conserved for
reaction to occur
CLASSIFICATION OF PERICYCLIC REACTIONS
Pericyclic Reactions are broadly classified into
five different categories:
[Link] Reactions
[Link] Reactions
[Link] Rearrangement
[Link] Reactions
[Link] Transfer Reactions
METHODS OF PERICYCLIC REACTIONS
ANALYSIS
1. Orbital Symmetry Correlation Method
2. The Frontier Orbital Method
3. Transition State Aromaticity Method
Frontier Orbital Treatment of
Pericyclic Reactions
A Frontier Orbital: is the highest-energy occupied orbital
or the lowest-energy unoccupied orbital in a molecule.
•Such orbitals have a large influence on chemical
properties of the molecules
A Molecular Orbital is a mathematical function
describing the wave-like behaviour of an electron in a
molecule.
•It is used to determine the probability of finding an
electron in any specific region
The frontier molecular orbitals of a compound
are at the “frontier” of electron occupation:
The highest-energy occupied molecular
orbital (HOMO)
The lowest-energy unoccupied molecular
orbital (LUMO)
HOMO: is the nucleophilic or electron
donating orbital; while the
LUMO: is the electrophilic and electron
accepting orbital
Pericyclic Reactions can only occur if the symmetries
of the ∏ orbitals in the reactants and the products
match.
[Link] reactions are referred to as symmetry allowed
reactions.
[Link] they do not match it is symmetry forbidden
reaction
3.A molecular orbital is symmetry if the signs on each
side of the vertical plane are the same
Frontier Molecular Orbital Theory
The theory explained chemical reactivity in
terms of interaction
•Highest Occupied MOs (HOMOs),
•Lowest Unoccupied MOs (LUMOs) and
•Singly Occupied MOs (SOMOs)
HOMO + LUMO -> bonding MO
HOMO + HOMO -> antibonding MO
LUMO + LUMO -> null interaction (no electrons)
SOMO + SOMO -> bonding MO
For example, ψ1 of ethene, the bonding molecular orbital is
symmetric; ψ2, the antibonding molecular orbital is antisymmetric.
Molecular orbital (MO) theory describes bonds as the mathematical
combination of atomic orbitals that forms a new set of orbitals called
molecular orbitals (MOs).
The number of atomic orbitals used equals the number of molecular orbitals
formed.
Since pericyclic reactions involve " bonds, let’s examine the molecular
orbitals that result from p orbital overlap in ethylene, 1,3-butadiene, and
1,3,5-hexatriene, molecules that contain one, two, and three " bonds,
respectively.
Ethylene
•The " bond in ethylene (CH2––CH2) is formed by side-by-side overlap of two p
orbitals on adjacent carbons. Two p orbitals can combine in two different ways. As
shown in Figure below,
•When two p orbitals of similar phase overlap, a " bonding molecular orbital
(designated as ψ1) results.
•Two electrons occupy this lower-energy bonding molecular orbital. When two p
orbitals of opposite phase combine, a "* antibonding molecular orbital (designated as
ψ2*) results.
•A destabilizing node occurs when two orbitals of opposite phase combine.
The symmetry of the π molecular orbitals always changes in the
following order: symmetric–antisymmetric– symmetric, etc.
Thus, ψ1 is symmetric, and ψ2 is antisymmetric. He Figure
below shows the bonding and antibonding molecular orbitals of
1,3-butadiene.
1,3-Butadiene
•The two " bonds of 1,3-butadiene (CH2––CH–CH––CH2) are formed by overlap
of four p orbitals on four adjacent carbons.
•As shown in Figure below, four p orbitals can combine in four different ways to
form four molecular orbitals designated as ψ1–ψ4.
•Two are bonding molecular orbitals (ψ1 and ψ2), and two are antibonding
molecular orbitals (ψ3* and ψ4*).
•The two bonding MOs are lower in energy than the p orbitals from which they are
formed, whereas the two antibonding MOs are higher in energy than the p orbitals
from which they are formed.
• In the ground-state electronic arrangement, the four " electrons occupy the two
bonding molecular orbitals.
• The highest energy orbital that contains electrons is called the highest occupied
molecular orbital (HOMO). In the ground state of 1,3-butadiene, ψ2 is the HOMO.
• The lowest energy orbital that contains no electrons is called the lowest
unoccupied molecular orbital (LUMO). In the ground state of 1,3-butadiene, ψ3*
is the LUMO.
Frontier molecular orbital theory considers only the signs of the wave
functions at the terminal carbon atoms of the HOMO and LUMO.
The HOMO of 1,3-butadiene is ψ2. It is antisymmetric.
As we noted earlier, this means that the signs of the wave functions of
the contributing terminal 2p atomic orbitals are reversed on opposite
sides of the reference vertical plane.
In all cases, MOs are either symmetric or antisymmetric with respect to
this plane.
The LUMO of 1,3-butadiene is ψ3. It is symmetric.
FMO Theory
Explanation of the Diels-Alder
Reaction
The alkene (dienophile) component has two electrons is a "single" π-
bond. FMO theory identifies the HOMO and LUMO components of this
system:
Likewise, the diene which has four electrons in is
conjugated π-system can have its HOMO and LUMO
identified within FMO theory:
If we examine the phases at the ends (termini) of the diene and
dieneophile we find that the LUMO/HOMO interactions are phase
matched:
Notice that the phases match whichever species is defined as the
HOMO or LUMO. In reality, the electron rich species reacts via its
HOMO and the electron poor species via its LUMO.
In the FMO diagrams above, the sizes or coefficients, are all the
same size, but usually they are of different sizes. The rule is that
the coefficients match as well: small with small and large with
large:
MODULE 2
Aromatic transition state treatment:
Huckel/Mobius transition states
• When the molecular orbitals of conjugated systems in which the
overlap of the p atomic orbitals (and therefore the electrons) are in a
LOOP such orbitals are said to exhibit Aromaticity
• we only need energies of cyclic M.O.'s, we do not need their
symmetry/phase information
• here we are dealing with cyclic loop pi-molecular orbitals and we will
find that they have degeneracies (orbitals of equal energies)
• In pericyclic reactions most stable electronic arrangement occurs when all of
the bonding molecular orbitals are filled such as in benzene and naphthalene
.
• These systems are considered to be aromatic.
• The connotation of the word is that the pi electrons of aromatic molecules
possess unusual stability in comparison to pi electrons in simple alkenes.
• A simple formula that indicates the number of pi electrons required for
a cyclic system to be considered aromatic is commonly referred to
as Hückel's 4n+2 rule;
• which states that cyclic planar molecules in which each atom has a p
orbital are aromatic if they contain 4n + 2 pi electrons.
• Here n is an integer, 0,1,2,3,...., that represents the number of sets of
degenerate bonding orbitals in the MO diagram of the molecule.
Hückel’s rule is an electronic criterion for aromaticity, and is based
on the configuration of the pi electrons.
Another characteristic of aromatic compounds is a relatively large
HOMO-LUMO gap, which indicates the absence of high-energy,
reactive electrons,
An aromatic molecule contains a cyclic array of orbitals in which
there are 4n + 2 electrons.
While anti-aromatic molecules are those in which the HOMO are not
completely filled, like those shown for cyclobutadiene and
cyclooctatretraene.
Here the connotation is that the pi electrons in anti-aromatic molecules are
less stable than their counterparts in simple alkenes. In the most common
situations anti-aromatic molecules contain 4n pi electrons, i.e. 0, 4, 8, 12, .....
electrons
The Möbius–Hückel treatment is not dependent on symmetry and only
requires counting the number of plus-minus sign inversions in proceeding
around the cyclic array of orbitals.
Where one has zero or an even number of sign inversions there is a
Hückel array.
Where an odd-number of sign inversions is found a Möbius array is
determined to be present.
Count the number of electrons in the cyclic array of orbitals. Hückel
systems are aromatic with 4n+2 π electrons, anti-aromatic with 4n
electrons.
Moebius systems are the reverse - they are aromatic with 4n
electrons and anti-aromatic with 4n+2 electrons
if the transition state is aromatic, then the reaction is
thermally allowed. If the transition state is anti-aromatic, a
photochemical process is required.
MODULE 3
CYCLOADDITION REACTIONS
• Cycloaddition reactions involve the combination of two
molecules to form a new ring.
• A cycloaddition reaction is a reaction in which the addition of
two π reactants form a cyclic compound.
• Concerted pericyclic cycloadditions involve reorganization of the
–electron systems of the reactants to form two new bonds.
• Cycloadditions are bimolecular reaction in which two π systems
interact to form two σ bonds and a new π bond in the
cycloadduct (cyclic compound).
Examples might include
•cyclodimerization of alkenes,
•cycloaddition of allyl cation to an alkene, and
• the addition reaction between alkenes and dienes (Diels-
Alder reaction).
CHARACTERISTICS OF CYCLOADDITION REACTIONS
•The cyclic compound has σ bonds at the ends of the
π components and
• concomitant reduction in π length in each
1. Cycloaddition reactions are reversible. The reverse reaction is possible
by a suitable choice of substrates and reaction conditions.
The reverse cycloaddition is called retro-cycloaddition or cycloreversion.
Retro-cycloaddition is unimolecular and commonly, Δσ = − 2.
2. The cycloadditions are designated by electron and atom conventions.
Electron convention: By electron convention, a cycloaddition is
designated as [l + m] cycloaddition, where l and m denote the number of
electrons involved in the two components.
Atom convention: By atom convention, a cycloaddition is designated as
(l + m) cycloaddition wherein l and m indicate the number of atoms
involved in the two components.
Thus, the designation [l + m] describes the number of electrons
participating in the cycloaddition, while (l + m) indicates the number of
atoms.
The electron convention is more important as it relates to the mechanism
of the reaction. The atom convention, however, identifies the ring size of
the product.
TYPES OF CYCLOADDITION REACTIONS
1. THERMAL CYCLOADDITION:
•Thermal cycloadditions are those cycloadditions where the reactants are in the ground
electronic state.
•They usually have (4n + 2) π electrons participating in the starting material, for some
integer n.
•These reactions occur for reasons of orbital symmetry
•There are a few examples of thermal cycloadditions which have 4n π electrons (for
example the [2 + 2]-cycloaddition). The dimerisation of ketene, in which the p
orbitals allows the reaction to proceed via a crossed transition state.
2. PHOTOCHEMICAL CYCLOADDITION:
•Cycloadditions in which 4n π electrons participate can also occur via photochemical
activation.
•Here, one component has an electron promoted from the HOMO (π bonding) to the
LUMO (π* antibonding).
•Example is the photochemical dimerization of cinnamic acid
Diels-Alder reactions
•The Diels-Alder reaction exists in a huge range of forms, including the
• Inverse electron-demand Diels–Alder reaction,
•Hexadehydro Diels-Alder reaction and
•The related alkyne trimerisation.
•The reaction can also be run in reverse in the retro-Diels–Alder reaction
Huisgen cycloadditions
The Huisgen cycloaddition reaction is a (2+3)cycloaddition.
Nitrone-olefin cycloaddition
The Nitrone-olefin cycloaddition Is a (3+2)cycloaddition
Iron-catalyzed 2+2 olefin cycloaddition
•Iron catalysts contain a redox active ligand in which the central iron
atom can coordinate with two simple, unfunctionalized olefin double
bonds.
•This gives it the flexibility to engage in binding the double bonds as
they undergo a cyclization reaction,
•generating a cyclobutane structure via C-C reductive elimination;
•alternatively a cyclobutene structure may be produced by beta-
hydrogen elimination.
Cheletropic reactions
•Cheletropic reactions are a subclass of cycloadditions.
•The key distinguishing feature of cheletropic reactions is that on one of
the reagents, both new bonds are being made to the same atom.
•The classic example is the reaction of sulfur dioxide with a diene
Formal cycloadditions
•When in a cycloaddition charged or radical intermediates are
involved or when the cycloaddition result is obtained in a series
of reaction steps they are sometimes called formal cycloadditions
to make the distinction with true pericyclic cycloadditions.
•One example of a formal [3+3]cycloaddition between a cyclic
enone and an enamine catalyzed
ELECTROCYCLIC REARRANGEMENT
An electrocyclic reaction is a type of pericyclic rearrangement where the net
result is one pi bond being converted into one sigma bond or vice versa.
These reactions are usually categorized by the following criteria:
•Reactions can be either photochemical or thermal
•Reactions can be either ring-opening or ring-closing (electrocyclization).
•Depending on the type of reaction (photochemical or thermal) and the
number of pi electrons, the reaction can happen through either a conrotatory
or disrotatory mechanism.
•The type of rotation determines whether the cis or trans isomer of the
product will be formed
Cyclizations reactions involving only single molecules, that
is, intramolecular cyclization are called electrocyclic rearrangements.
Two examples follow to show cyclization of a diene and a triene:
A striking feature of thermal electrocyclic reactions that proceed by
concerted mechanisms is their high degree of stereospecificity.
Thus when cis-3,4-dimethylcyclobutene is heated, it affords only one of
the three possible cis-trans isomers of 2,4-hexadiene, namely, cis,trans-
2,4-hexadiene:
When a cyclobutene is so constituted that conrotation cannot occur for
steric reasons, then the concerted reaction cannot occur easily.
It is of great interest and importance that,
with systems of 4n+2 electrons, the
groups move in opposite directions
(↶↷↶↷ or ↷↶↷↶, disrotatory). For
example,
In this case, the disrotation of the groups toward one another would
lead to the cis,cis,cis product. Because this product is not formed, it
seems likely that rotation of the methyl groups toward each other must
be sterically unfavorable:
• Our problem is to understand why it is that concerted 4n
electrocyclic rearrangements are conrotatory, whereas the
corresponding 4n+2 processes are disrotatory.
• The conrotatory processes are related to the Möbius molecular
orbitals and the disrotatory processes are related to Hückel molecular
orbitals. Consider the electrocyclic interconversion of a 1,3-diene and
a cyclobutene.
• In this case, the Hückel transition state (one having an even number
of nodes) is formed by disrotation, but is unfavorable with four (that
is, 4n ) electrons:
In contrast, the Möbius transition state (one having an odd number of
nodes) is formed by conrotation and is favorable with four (4n)
electrons
The factors that control if and how these cyclization and rearrangement
reactions occur in a concerted manner can be understood from the
aromaticity or lack of aromaticity achieved in their cyclic transition
states.
•For a concerted pericyclic reaction to be thermally favorable, the
transition state must involve 4n+2 participating electrons if it is a
Hückel orbital system, or 4n electrons if it is a Möbius orbital system.
•A Hückel transition state is one in which the cyclic array of
participating orbitals has no nodes (or an even number) and
•a Möbius transition state has an odd number of nodes
Procedure to predict the feasibility and the stereochemistry
of thermally concerted reactions involving cyclic transition states
• The first step of the procedure is to draw the orbitals as they are
expected to be involved in the transition state
• The second step is to determine whether the transition states are
Hückel or Möbius from the number of nodes.
• we evaluate the transition states according to the 4n or 4n+2 rule.
• the stereochemistry of the reaction can be predicted when we have
predicted which transition state is the favored one.
The stereochemical results of electrocyclic and cycloaddition reactions
carried out photochemically often are opposite to what is observed for
corresponding thermal reactions. However, exceptions are known and
the degree of stereospecificity is not always as high as in the thermal
reactions.
MODULE 4
INTRODUCTION TO SIGMATROPHIC SHIFTS
Sigmatrophic Shift or Reactions is the molecular rearrangements in which a σ-
bonded atom or group, flanked by one or more π-electron systems, shifts to a
new location with a corresponding reorganization of the π-bonds.
CHARACTERISTICS OF SIGMATRPHIC SHIFTS
•The total number of σ-bonds and π-bonds remain unchanged
•In a sigmatropic rearrangement one bond is being broken while another bond is
being formed across a p system.
•Processes with 2- and 6-electron (Huckel, 4n+2) are allowed suprafacially, 4-
electron processes must occur antarafacially (Moebius, 4n).
•The numbering system [m,n] gives the number of atoms between the bond being
broken and the bond being formed in the two directions.
•In a sigmatropic reaction a σ bond 'migrates' across a conjugated system to a new
site. If '[n,m] sigmatropic rearrangement' has n = 1, then one end of the bond that
moves remains attached to its original atom — the n refers to the fact that the other
end of the bond migrates across n atoms. This type of reaction often features a
migrating C–H bond, i.e. a [1,n] hydrogen shift
Example 1: Features a suprafacial [1,5] shift. If we add one more C=C π bond (two
more p electrons), the observed thermal [1,7] shift is antarafacial — the C–H starts
'above' but ends up 'below' and the H appears to migrate from one face of the π
system to the other. This will only happen if the molecule can adopt the
conformation required for the rearrangement