23.4 Enolates of Unsymmetrical Carbonyl Compounds

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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.

Figure 1.png

Kinetic Enolates

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

Figure 2.png

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.

Figure 3.png

Problems

Contributors

Prof. Steven Farmer (Sonoma State University)
Layne A. Morsch - University of Illinois Springfield