Introductory Organic Chemistry

2325.001

Chapter 15 – Conjugated systems

Prof. Christina Thompson

February 8th, 2018
Lecture 10
 Examples
CH3ONa
O
CH3OH

H+
O
CH3OH

Li

O
THF

O OH

OH
Relative Stabilities
 Lets talk about Orbitals

• Standing wave vibrates in fixed location.

• Wave function, ψ, is a mathematical description of
size, shape, and orientation.
• Amplitude may be positive or negative.
• Node: Amplitude is zero.

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 σ-Bonding

Formation of a σ bonding MO: When the 1s orbitals of two hydrogen

atoms overlap in phase with each other, they interact constructively to
form a bonding MO.
 σ* - Bonding

Formation of a σ* antibonding MO: When two 1s orbitals overlap out of

phase, they interact destructively to form an antibonding MO.
Molecular Orbital Diagram of a σ-bond
 π-π Bonding

The sideways overlap of two parallel p orbitals leads to a π bonding

MO and a π* antibonding MO. A pi (π) bond is not as strong as most
sigma bonds.
 π Orbitals and Multiple Bonds

• A double bond (two pairs

of shared electrons)
consists of a sigma bond
and a pi bond.
• A triple bond (three pairs
of shared electrons)
consists of a sigma bond
and two pi bonds.

© 2013 Pearson Education, Inc.

 Buta-1,3-diene

• The C2—C3 single bond is shorter than 1.54 Å.

• Electrons are delocalized over the molecule.
• There is a small amount of overlap across the central
C2—C3 bond, giving it a partial double bond
character.
 Ethylene π MO

• The combination of two p orbitals must give two molecular

orbitals.
• Constructive overlap is a pi bonding (π) MO.
• Destructive overlap is an antibonding (π*) MO.
 Ethylene π MO  
• With  the  MO  we  can  draw  the  electronic  
configura4on  of  ethylene  
• 2  electrons  in  the  pi  bond,  so  two  electrons  
into  the  system.  
• Most  stable  systems  have  the  bonding  orbitals  
full,  and  the  an4-­‐bonding  orbitals  empty.    
 π1 MO for Buta-1,3-diene

• 4 p orbitals, so 4
molecular orbitals.
• Lowest energy.
• All bonding
interactions.
• Electrons are
delocalized over
four nuclei.
 π2 MO for Buta-1,3-diene

• Two bonding
interactions.
• One antibonding
interaction.
• This is a bonding
MO.
• Higher energy than
π1 MO and not as
strong.
 π3* MO for Buta-1,3-diene

• Two antibonding
and one bonding
interaction.
• Two nodes.
• Vacant in the
ground state.
 π4* MO for Buta-1,3-diene

• Three nodes.
• Strongly
antibonding.
• Highest energy
MO.
• Vacant at ground
state.
MO for Buta-1,3-diene and Ethylene

• The bonding MOs of

both buta-1,3-diene and
ethylene are filled and
the antibonding MOs
are empty.
• Buta-1,3-diene has
lower energy than
ethylene.
• This lower energy is the
resonance stabilization
of the conjugated diene.
 Conformations of Buta-1,3-diene
• For the p bonds to be aligned with overlap,
the molecule must be flat.
• The s-trans conformer is more stable than the
s-cis by 12 kJ/mol (2.8 kcal/mol).
• Easily interconvert at room temperature.
 Allylic Position

• Remember the allylic position is the sp3

hybridized carbon directly adjacent to an sp2
hybridized carbon.
• The positive charge is delocalized over two
carbons by resonance, giving the allyl cation
more stability than nonconjugated cations.
 The Allylic Position

• Geometric structure of
the allyl cation, allyl
radical, and allyl anion.
• The three p orbitals of
the allyl system are
parallel to each other,
allowing for the
extended overlap
between C1–C2 and
C2–C3.
MO for Allylic Species
 Allylic Anions

• The allylic anion has two electrons in the π2

MO.
• The negative charge is focused on the
outside, which is what we see in the
resonance depiction.
• Each carbon on the outside holds half of the
negative charge, the one in the middle does
not hold any.
 Addition Reactions in Conjugated
Systems

• Remember that alkenes can react with acid to

make carbocations.
• Dienes react to make allylic cations.
• The nucleophile can then react at one of two
places.
• Addition of HBr to buta-1,3-diene produces 3-
bromobut-1-ene (1,2-addition) and 1-
bromobut-2-ene (1,4-addition).
Conjugated Addition
 Thermodynamic vs Kinetic Control
• The  Kine4c  product  is  the  one  that  forms  fastest.  
• The  Thermodynamic  product  is  the  most  stable.  
• These  are  not  always  the  same.    
Relative Stabilities
 Kinetic Control
• Transition state for the 1,2-addition has a lower Ea
because it is a more stable secondary carbocation.
• The 1,2-addition will be the faster addition at any
temperature.
• The nucleophilic attack of the bromide on the C2
allylic carbocation is irreversible at this low
temperature.
• The product that forms faster predominates (kinetic
product).
• Because the kinetics of the reaction determines the
product, the reaction is said to be under kinetic
control.
 Thermodynamic Control
• The 1,2-addition is still the faster addition, but at 40 °C,
the bromide attack is reversible.
• The 1,2-product ionizes back to the allylic cation.
• At 40 °C an equilibrium is established, which favors the
most stable product.
• The 1,4-addition is the most stable product
(thermodynamic product) because it has a more
substituted double bond.
• Because the thermodynamics of the reaction
determines the product, the reaction is said to be under
thermodynamic control.
 Allylic Brominations
• Remember  that  we  form  allylic  radicals  when  
we  do  radical  bromina4ons.    
Initiation step:

Propagation steps:
 Brominations with NBS

• Remember that alkenes can react with HBr to add

HBr across the double bond.
• To encourage allylic substitution have a low
concentration of Br2 around, use light or peroxides to
form radicals.
• NBS provides a low, constant concentration of Br2.
 SN2 reactions at Allylic Centers
• Allylic  stabiliza4on  of  the  charges  in  the  
transi4ons  state  make  allylic  posi4ons  faster  
for  SN2  reac4ons.    
 Pericyclic Reactions

• Reac4ons  containing  simultaneous  bond  

forma4on  or  breakage  with  a  ring  of  interac4ng  
orbitals.  
• Orbitals  must  form  a  con4nuous  loop,  therefore  
all  adjacent  orbitals  must  be  able  to  overlap.    
• If  the  resul4ng  bond  is  lower  in  energy  than  the  
star4ng  bonds,  then  the  reac4on  is  favorable.    
• With  conjugated  π  systems  we  only  worry  about  
the  π-­‐electrons.    
 Diels-Alder Reaction

• One-step, concerted mechanism.

• A diene reacts with an electron-poor alkene
(dienophile) to give cyclohexene or
cyclohexadiene rings.
 HOMOs and LUMOs

• The  molecular  orbital  highest  in  energy  is  the  

HOMO  
• The  MO  with  the  lowest  energy  is  the  LUMO.  
HOMO LUMO Interactions
 MO Overlap

• Diene contributes electrons from its highest energy

occupied orbital (HOMO).
• Dienophile receives electrons in its lowest energy
unoccupied orbital (LUMO).
• We MUST have orbital symmetry for reaction to take
place.
 Relative Stabilities

• [2 + 2] cycloaddition of two ethylenes to form

cyclobutene has antibonding overlap of HOMO and
LUMO.
• Therefore this reaction is said to be symmetry
unallowed, and does not take place under normal
thermal conditions.
 Light Induced 2+2

• Absorption of correct energy photon will promote an

electron to an energy level that was previously
unoccupied.
• Changing these energies makes the reaction
allowed.
 Diels-Alder Reactions
• Type of pericyclic reaction.
• Named after Otto Diels and Kurt Alder. They
received the Nobel prize in1950.
• The reaction is between a diene and an
electron-deficient alkene (dienophile).
• Produces a cyclohexene ring.
• The Diels–Alder is also called a [4 + 2]
cycloaddition because a ring is formed by the
interaction of four pi electrons of the alkene
with two pi electrons of the alkene or alkyne.
Relative Energies of HOMO and LUMO
Examples of Products
 Tuesday!

• More  on  Chapter  15,  conjugated  systems  

• We’ll  maybe  start  Chapter  16  on  Aroma4c  
compounds