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    Stereoselective and Stereospecific Reactions

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    Hunzala
    The document discusses stereoselective and stereospecific reactions. Stereoselective reactions produce stereoisomeric products but favor one isomer over others due to reaction mechanism. Examples given are hydride reduction and bromination of alkenes. Stereospecific reactions give stereoisomeric products from stereoisomeric reactants through inversions or additions that maintain configuration. Epoxidation and dihydroxylation and hydroboration are discussed as being stereospecific.

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    Stereoselective and Stereospecific Reactions

    Uploaded by

    Hunzala
    2K views20 pages
    The document discusses stereoselective and stereospecific reactions. Stereoselective reactions produce stereoisomeric products but favor one isomer over others due to reaction mechanism. Examples given are hydride reduction and bromination of alkenes. Stereospecific reactions give stereoisomeric products from stereoisomeric reactants through inversions or additions that maintain configuration. Epoxidation and dihydroxylation and hydroboration are discussed as being stereospecific.

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    The document discusses stereoselective and stereospecific reactions. Stereoselective reactions produce stereoisomeric products but favor one isomer over others due to reaction mechanism. Examples given are hydride reduction and bromination of alkenes. Stereospecific reactions give stereoisomeric products from stereoisomeric reactants through inversions or additions that maintain configuration. Epoxidation and dihydroxylation and hydroboration are discussed as being stereospecific.

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    © All Rights Reserved
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    2K views20 pages

    Stereoselective and Stereospecific Reactions

    Uploaded by

    Hunzala
    The document discusses stereoselective and stereospecific reactions. Stereoselective reactions produce stereoisomeric products but favor one isomer over others due to reaction mechanism. Examples given are hydride reduction and bromination of alkenes. Stereospecific reactions give stereoisomeric products from stereoisomeric reactants through inversions or additions that maintain configuration. Epoxidation and dihydroxylation and hydroboration are discussed as being stereospecific.

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    Stereoselective and Stereospecific

    Reactions
    Stereoselective Reactions

    • Many reactions can produce two or more stereoisomeric

    products. If a reaction shows a preference for one of the

    stereoisomers, it is stereoselective Stereoselectivity is intimately

    related to the mechanism of the reaction.


    Examples of Stereoselective Reactions
    Examples of Stereoselective Reactions
    Examples of Stereoselective Reactions
    H. W. Thompson, J. Org. Chem., 36, 2577 (1971).

    H. W. Thompson, E. McPherson, and B. L. Lences, J. Org. Chem., 41, 2903


    Hydride Reduction of Cyclic Ketones
    The chair conformation of cyclohexanone places the carbonyl
    group in an unsymmetrical environment.

    The axial face has C(2 6)−Heq bonds that are


    nearly eclipsed with the C=O bond and the
    C(3,5)-diaxial hydrogens point toward the
    trajectory for reagent approach.
    The equatorial face has axial C−H bonds at an
    angle of roughly 120 to the carbonyl plane.
    There is more steric bulk, including the 3,5-
    axial hydrogens, on the axial face.

    It is observed that small nucleophiles prefer to approach the carbonyl


    group of cyclohexanone from the axial direction, even though this is a
    more sterically congested approach.
    Hydride Reduction of Cyclic Ketones
    • Torsional effects are believed to play a major role in the preference for
    axial approach. In the reactant conformation, the carbonyl group is
    almost eclipsed by the equatorial C(2) and C(6) C−H bonds.
    • This torsional strain is relieved by axial attack, whereas equatorial
    approach increases strain because the oxygen atom must move through
    a fully eclipsed arrangement.
    • More bulky reducing agents usually approach the cyclohexanone
    carbonyl from the equatorial direction.
    • This is called steric approach control and is the result of van der Waals
    repulsions with the 3,5-axial hydrogens.
    Hydride Reduction of Cyclic Ketones
    Stereospecific Reactions
    • Some reactions are stereospecific, that is reactions in which
    stereoisomeric reactants each provide stereoisomeric
    products.
    • For example, the SN2 substitution reaction results in an
    inversion of the configuration. It is a stereospecific reaction.
    • The R-reactant gives the S-product and the S-reactant gives
    the R-product
    Bromination of Alkenes
    • The addition of bromine is usually stereospecifically anti for
    unconjugated disubstituted alkenes and therefore the Z- and E-
    alkenes lead to diastereomeric products.
    Bromination of Alkenes
    Epoxidation and Dihydroxylation of Alkenes
    • An example of syn addition is osmium tetroxide– catalyzed
    dihydroxylation.
    • This reaction is carried out using a catalytic amount of OsO4, under
    conditions where it is reoxidized by a stoichiometric oxidant.
    • The most common oxidants are t-butyl hydroperoxide, potassium
    ferricyanide, or an amine oxide.
    • The two oxygens are added from the same side of the double bond. The
    key step in the reaction mechanism is a 3+2 cycloaddition that ensures
    the syn addition.
    Epoxidation and Dihydroxylation of Alkenes
    • Alkenes can be converted to diols with overall anti addition by a two-step
    sequence involving epoxidation and hydrolysis.
    • The epoxidation is a syn addition that occurs as a single step.

    • When epoxidation is followed by hydrolytic ring opening, the configuration


    of the diols is determined by the configuration of the alkene, usually with net
    anti dihydroxylation.
    • The hydrolysis reaction proceeds by back-side epoxide ring opening.
    Hydroboration-Oxidation Hydroboration
    • Hydroboration-Oxidation Hydroboration is a stereospecific syn addition.

    • The reaction occurs by an electrophilic attack by borane or alkylborane


    on the double bond with a concerted shift of hydrogen.

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