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Lecture9 Pericyclic3

The document outlines selection rules for cycloaddition reactions, emphasizing the importance of facial interactions and the allowedness of reactions based on electron count and mode of addition. It discusses the Diels-Alder reaction, including requirements for reactivity, the influence of substituents on reactivity, and stereospecificity rules such as the Cis-rule and Alder Endo Rule. Additionally, it highlights synthetic applications and provides practice problems for understanding these concepts.

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Brian Mackwan
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7 views29 pages

Lecture9 Pericyclic3

The document outlines selection rules for cycloaddition reactions, emphasizing the importance of facial interactions and the allowedness of reactions based on electron count and mode of addition. It discusses the Diels-Alder reaction, including requirements for reactivity, the influence of substituents on reactivity, and stereospecificity rules such as the Cis-rule and Alder Endo Rule. Additionally, it highlights synthetic applications and provides practice problems for understanding these concepts.

Uploaded by

Brian Mackwan
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Recap- Selection Rules for Cycloaddition

Cycloadditions involve facial interactions and not side by


side interactions
System Mode of Allowedness of the reaction
(total no. of addition
electrons) Thermal Photochemical

4n s/s forbidden allowed

4n s/a allowed forbidden

4n+2 s/s allowed forbidden

4n+2 s/a forbidden allowed

(n = natural number)
Since s/a mode is difficult to achieve mainly the s/s
mode is observed
2π + 2π Cycloaddition

Products formed due to suprafacial-suprafacial interactions


2π + 2π Intramolecular Cycloaddition
Interesting Synthetic Applications

Provides access to strained caged compounds


4π + 2π Cycloaddition
Diels-Alder Reaction

diene dienophile adduct


Thermal cycloaddition between a conjugated diene and a dienophile
Discovered by Otto Diels and Kurt Alder (Nobel prize 1950)

Diels Alder
Reactivity - Diels-Alder Reaction
Requirement
Diene should be in a cisoid (s-cis) conformation

Transoid dienes are unreactive

Normally isomerization possible

Unreactive as transoid structure is locked


[4π + 2π]

Diene Dienophile
(2 double (likes diene)
bonds)

Commonly observed – Dienes – electron rich


Dienophile – electron deficient

‘Normal’ electron demand Diels Alder Reactions


Effect of Substituent on Reactivity
Electron releasing groups - Raise HOMO and LUMO energy

Electron withdrawing groups - Lower HOMO and LUMO energies


Improve Decrease ERG on diene
D-A rate HOMO-
LUMO gap EWG on dienophile
ΔE2 < ΔE1
LUMO2 More
efficient
ΔE1 LUMO2
ΔE2 reaction
HOMO1
HOMO1

E
Diene Dienophile Dienophile Diene
Small Activity
Compare the order of reactivity for these dienes

Planar Alkyl – Not planar EWG –


Constrained HOMO inc. Near S-cis HOMO dec.
S-cis
Cis-Rule in Diels-Alder Reactions
Suprafacial-Suprafacial Interaction
Cis dienophile Adduct with cis subs.

Trans dienophile Adduct with trans subs.

Rule holds true for dienes as well !


Cis Rule
The Transition State
Another View
Diels Alder reaction – Highly Stereospecific
Alder Endo Rule
Dienophile approaches the diene preferentially in the endo mode so as
to allow maximum spatial overlap of the unsaturated centers of the
diene and dienophile

Endo product Exo product

Endo approach - Favoured Exo approach


Why Endo Approach?
Endo Approach

Secondary Orbital Interactions


Transition State Stabilized!
Exo Approach

Secondary Orbital Interactions difficult


(Orbitals far away from each other!)
[4+2] Cycloaddition Reactions:The Alder Endo Rule

Excellent endo selectivity for maleic anhydride

16
Let us try to write the products
Regioselectivity

Favoured

Favoured
Regioselectivity - Examples
Recap - [4π + 2π] Cycloaddition
Reactivity Selectivity
• Cis-rule – Relative stereochem
• S-Cis Conformation required diene or dienophile

required

• Endo-rule - Relative stereochem


• ERG – Diene (HOMO) diene-dienophile
• Regioselectivity
EWG – Dienophile (LUMO)
syn
out

in
Problems for Practice

Intra-molecular

Don’t get confused: Remember the basics ☺


More Problems
What is the product?

What is the mechanism?


Synthetic Utility
Synthesis of Basketene
Synthesis of Endiandric acid
Recap - [4π + 2π] Cycloaddition
Reactivity Selectivity
• Cis-rule – Relative stereochem
• S-Cis Conformation required diene or dienophile

required

• Endo-rule - Relative stereochem


• ERG – Diene (HOMO) diene-dienophile
• Regioselectivity
EWG – Dienophile (LUMO)
syn
out

in
Final Exam

Mark your calendars for Final Organic Exam


November 26, 2022
9:30 – 11:30 am
Topics
covered
here quite
logical!!!

http://www.chemistry-blog.com/2010/05/05/calvin-and-hobbes-on-chemistry/
All the Best!!!!!
Philosophy on teaching-learning and role
of a teacher beautifully captured here –
Enjoy !
https://youtu.be/X7tHZaWP6DY

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