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Aong Subayu
Aong Subayu
Aong Subayu
Simple Mechanism
The mechanism for a pericyclic reaction
How many electrons are moving through aligned p orbitals during the
transition state? tiga
By Huckel’s Rule, how would you characterize the transition state?
Cycloadditions involve the interaction of HOMO of one molecule with LUMO on the
other.
↿⇂
↿⇂
↿⇂
LUMO
bonding
antibonding
HOMO
What is wrong?
Karena sikloadisi ini melibatkan HOMO dari salah satu etilen untuk
tumpang tindih dengan LUMO etilen satunya. Interaksi antibonding
(tumpeng tindih ikatan yang berbeda) meningkatkan energi aktivasi,
sehingga reaksi sulit dilakukan dan diklasifikasikan sebagai symmetry-
forbidden.
Draw the resonance structures that illustrate that this diene is really a
nucleophile and this dienophile is really an electrophile.
Using the MO mixing diagrams for each reaction above, explain why
DE (LUMO- HOMO) decreases in each successive example.
Practice Problems:
1. Show the products of these reactions including regiochemistry:
2. Show the reagents needed to prepare these products through Diels-
Alder Reactions.
A pericyclic reaction involving 4n electrons is thermally allowed if the orbitals add from
opposite faces (antarafacial).
What does the HOMO (SOMO) of ethene look like after excitation
with light?
Photochemical Condition
Photochemical Condition
Photochemical Condition
Thermal Condition
Photochemical Condition
Thermal Condition
Thermal Condition
Application Problems:
1. For the following electrocyclic reactions, draw out the HOMO (with
correct shading of orbitals), and predict the product (make sure to
include stereochemistry)
2. When allyl 2,6-dimethylphenyl ether is heated 4-
allyl-2,6- dimethylphenol is formed.
o Propose a mechanism for this reaction.
Now here are two analogous reactions that might have been expected
to produce simple alkenes or alkynes but do not:
Your tasks:
Photocatalytic Cycloadditions
This exercise looks at the evolving approach of one laboratory to adapt a
method of reactivity to a variety of systems.
Circle the orbitals that would interact with each other in a 2+2
cycloaddition.
In contrast, a Diels Alder reaction carried out by heating for 72 h at 150oC provided the
opposite regiochemistry.
Show which end of the diene and dienophile are more electron-rich,
and show how that changes under photocatalytic conditions. Dienofil
yang kaya electron yaitu pada cicin aril nya
Myrcene and fagaramide are natural products of F. heitzii. Comment
on the significance of this fact in terms of the biosynthesis of
heitziamide A.
The Yoon lab decided to turn to a new catalyst, shown below. It has an oxidation
potential of +0.89 V vs SCE.
Will this compound be more successful as an electron-transfer catalyst,
based on this data?
The strategy this time was to transfer energy, rather than an electron, from the
catalyst to the substrate. The excited iridium complex can form an excited state
triplet (via “inter-system crossing”), the energy of which is about 60 kcal/mol above
the ground state iridium complex.
That triplet can occasionally exchange energy with the styrene substrate, which also
has a triplet state about 60 kcal/mol above its ground state. This process is called
“photosensitization”. The excited styrene undergoes 2+2 cycloaddition.
How much energy does the catalyst have left after transferring
energy to the styrene?
Describe the electronic state of the iridium after the transfer has
occurred.