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    Lecture 7-8 (1)

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    organic ppt about diels alder

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    Lecture 7-8 (1)

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    purushottam.alcheringa
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    organic ppt about diels alder

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    organic ppt about diels alder

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    0 views27 pages

    Lecture 7-8 (1)

    Uploaded by

    purushottam.alcheringa
    organic ppt about diels alder

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    © All Rights Reserved
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    Diels-Alder Reaction A concerted combination of two π-electron systems to form a ring of atoms having

    two new σ bonds and two fewer π bonds is called a cycloaddition reaction.

    2+2 cycloaddition
    The cycloadditions that do occur thermally, for example, the Diels–Alder
    reaction, have (4n + 2 π) electrons in their ‘aromatic’ transition states

    The cycloadditions that do not occur thermally, for example the dimerization of
    alkenes and of dienes, have 4n ππ electrons in their ‘anti-aromatic’ transition states
    Difference Between Thermal and Photochemical Conditions

    The normal electronic configuration of a


    molecule is known as its ground state. In
    the ground state of 1,3-butadiene, the
    highest occupied molecular orbital (HOMO)
    is ψ2 and the lowest unoccupied molecular
    orbital (LUMO) is ψ3 . If a molecule absorbs
    light of an appropriate wavelength, the
    light will promote an electron from its
    ground-state HOMO to its LUMO (from ψ2
    to ψ3). The molecule is then in an excited
    state. In the excited state, the HOMO is ψ3
    and the LUMO ψ4 is In a thermal reaction
    the reactant is in its ground state; in a
    photochemical reaction the reactant is in
    ψ1 and ψ3 are symmetric molecular orbitals and ψ2 and ψ4 are an excited state.
    asymmetric molecular orbitals.
    Types of Pericyclic Reactions

    1. Cycloaddition reactions 2. Electrocyclic 3. Sigmatropic 4. Group transfer Reactions (Ene reaction)

    Electrocyclic Reactions

    An electrocyclic reaction is the


    concerted cyclization of a conjugated
    π-electron system by converting one
    π-bond to a ring forming σ-bond. The
    reverse reaction may be called
    electrocyclic ring opening.
    Electrocyclic
    the ground-state HOMO of a
    compound with an even number of
    conjugated double bonds is
    asymmetric, whereas the ground-state
    HOMO of a compound with an odd
    number of conjugated double bonds is
    symmetric.
    Conrotatory

    Disrotatory
    The symmetry of the HOMO of
    the compound undergoing ring
    closure controls the
    stereochemical outcome of an
    electrocyclic reaction.

    symmetry-allowed pathway is one in which in-phase orbitals overlap;


    a symmetry-forbidden pathway is one in which out-of-phase orbitals would overlap
    Woodward-Hoffman Rules for Electrocyclizations

    The conservation of orbital symmetry theory states that in-phase orbitals


    overlap during the course of a pericyclic reaction.
    What is the conformation of the energy maximum in the energy profile diagram for the
    ring inversion of cyclohexane.
    Draw the most stable conformation of cis-1,4-di-tertiarybutylcyclohexane.
    Predict the absolute configuration (R & S) of the following compounds P & Q.
    How many stereoisomers (including enantiomers) are possible for the
    following compound.
    Draw the major products (P & Q) in the following transformations.
    Arrange the following dienes in order of increasing reactivity in a Diels-Alder
    reaction.

    The correct order is


    Use Frontier Molecular Orbitals (FMOs) and explain why [2 + 2] cycloaddition
    between two alkenes under thermal conditions is forbidden.
    Explain why a 1,3-butadiene undergoes a [4+2] cycloaddition to give a six membered ring
    instead of undergoing a [4+4] cycloaddition to give an eight membered ring under thermal
    conditions.

    Molecular orbitals of 1,3-butadiene


    Under thermal conditions, for the diene system, the HOMO is Ѱ2 and the LUMO is Ѱ3

    [4+2] cycloaddition involves both bonding interactions and hence is thermally allowed

    [4+4] cycloaddition involves only one bonding interaction and hence is thermally forbidden.
    Draw the molecular orbitals for 1,3,5-hexatriene.
    Write the correct stereochemistry at the ring fusion of the product and explain the outcome.

    It is a triene system.

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