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21.5: Enolates of Unsymmetrical Carbonyl Compounds

  • Page ID
    28432
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    Enolate of Unsymmetrical Carbonyl Compounds

    Now let’s consider what happens when an unsymmetrical carbonyl is treated with a base. In the case displayed below there are two possible enolates which can form. The removal of the 2o hydrogen forms the kinetic enolate and is formed faster because it is less substituted and thereby less sterically hindered. The removal of the 3o hydrogen forms the thermodynamic enolate which is more stable because it is more substituted.

    Kinetic Enolates

    Kinetic enolates are formed when a strong bulky base like LDA is used. The bulky base finds the 2o hydrogen less sterically hindered and preferable removes it.

    Low temperature are typically used when forming the kinetic enolate to prevent equilibration to the more stable thermodynamic enolate. Typically a temperature of -78 oC is used.

    Thermodynamic Enolates

    The thermodynamic enolate is favored by conditions which allow for equilibration. The thermodynamic enolate is usually formed by using a strong base at room temperature. At equilibrium the lower energy of the thermodynamic enolate is preferred, so that the more stable, more stubstituted enolate is formed.

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    21.5: Enolates of Unsymmetrical Carbonyl Compounds is shared under a not declared license and was authored, remixed, and/or curated by LibreTexts.

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