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  • Chapter 6. Concerted Cycloadditions, Unimolecular Rearrangements, and Thermal Eliminations

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    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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    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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    10 views1 page

    Chapter 6. Concerted Cycloadditions, Unimolecular Rearrangements, and Thermal Eliminations

    Uploaded by

    Seungju Kang
    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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    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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