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Diels-Alder and Cycloaddition Reactions

This document summarizes various organic reaction mechanisms including: 1. Diels-Alder reactions which involve the [4+2] cycloaddition of dienes and dienophiles in a concerted process. The reaction favors endo products and can be catalyzed by Lewis acids. 2. [2+2] cycloadditions of ketenes and alkenes which can occur photochemically. 3. Sigmatropic rearrangements including [3,3]- and [2,3]-shifts which involve the migration of sigma bonds and usually occur in strained cyclic systems. 4. Thermal elimination reactions where the elimination of a group forms a new double bond or ring in an

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7 views1 page

Diels-Alder and Cycloaddition Reactions

This document summarizes various organic reaction mechanisms including: 1. Diels-Alder reactions which involve the [4+2] cycloaddition of dienes and dienophiles in a concerted process. The reaction favors endo products and can be catalyzed by Lewis acids. 2. [2+2] cycloadditions of ketenes and alkenes which can occur photochemically. 3. Sigmatropic rearrangements including [3,3]- and [2,3]-shifts which involve the migration of sigma bonds and usually occur in strained cyclic systems. 4. Thermal elimination reactions where the elimination of a group forms a new double bond or ring in an

Uploaded by

Seungju Kang
Copyright
© All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd

2017-12513 강승주

Chapter 6. Concerted Cycloadditions, Unimolecular 3. [2+2] Cycloadditions and Related Reactions Leading to
Rearrangements, and Thermal Eliminations Cyclobutane
Cycloaddition of ketenes and alkenes:
1. Diels-Alder Reactions
[4+2] cycloaddition: concerted, involving a single transition state

HOMO of diene / LUMO of dienophile


-> EDG on diene / EWG on dienophile facilitates reaction
Regioselectivity: controlled by substituents and their electronic effects
Photochemical additions allowed by orbital symmetry rules:

Preference of endo-adduct b/c secondary orbital interactions


between substituents on dienophile and diene p orbitals
Catalysis by Lewis acids: coordination with dienophile 4. [3,3]-Sigmatropic Rearrangements
Application: creation of cyclohexene ring

Diastereoselective Diels Alder: chiral auxiliaries reversible reactions: oxy-cope strongly catalyzed by base
Usually used in reactions that break strongly strained rings
Claisen rearrangement:

Exo-selective Diels-Alder: thermodynamic control/use of catalysts


Enantioselective catalysts:
modifications: orthoester Claisen rearrangements, allyl vinyl ethers
5. [2.3]-Sigmatropic Rearrangements

Neutral type: rearrangements of allylic sulfoxides, selenoxides, and


amine oxides
-> Coordination to boron controls stereochemistry
Intramolecular Diels-Alder also possible:
-> preferential endo TS
Rearrangement of Allylic Sulfonium and Ammonium Ylides:

Anionic type: rearrangements of carbanions of allylic ethers / Wittig

2. 1,3-Dipolar Cycloaddition reactions


1,3-dipolar compounds: compounds having π electron systems that
are isoelectronic with allyl or propargyl anions, consisting of two filled 6. Unimolecular Thermal Elimination Reactions
and one empty orbital -> reactions in which elimination to form a double bond or a new
-> reaction between 1,3-dipolar compounds and dipolarophiles ring occurs as a result of thermal activation
(usually alkenes/alkynes) Cheletropic elimination: reactions in which two bonds are broken at
a single atom

Stereospecific syn addition: because of concerted addition process


Decomposition of cyclic azo compounds:

Regioselectivity: electronic control / steric control


Synthetic applications: synthesis of heterocyclic molecules
Lewis acid catalysis possible: by lowering the LUMO energy of
dipolarophile. Some catalysts can also affect enantioselectivity

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