Chapter 20 Enolate Anions: Acyl Addition and Acyl Substitution

Carbonyl derivatives with a proton on an a-carbon react with a suitable base to generate a carbon nucleophile called an enolate anion. Enolate anions react as a nucleophile in acyl addition, acyl substitution and alkylation reactions. A powerful base such as an organolithium is required to remove the proton from nitrogen. An acid-base reaction is an equilibrium. The nature of the base plays a major role in the position of the equilibrium after deprotonation of an aldehyde or ketone. An aldol condensation with different ketones can lead to very interesting aldol products. The ability to control the equilibrium of an aldol condensation reaction was accomplished when non-nucleophilic bases were developed.

Aldehydes, Ketones and Enols

Enolate Anions

The u-Hydrogen and Electronic Effects

The Aldol Condensation

Mixed Aldol Condensations

Kinetic and Thermodynamic Conditions

Reaction Conditions and Equilibria

Return to Mixed Aldol Condensations

Intramolecular Aldol Condensation

Aldol Reactions

Acyl Substitution of Ester Enolates

Ester Enolates with Aldehydes and Ketones

Ester Enolate Anion Reactions

Malonic Esters and the Knoevenagel Reaction

Decarboxylation

Enolate Alkylation

Wittig Reaction

Stork Enamine Reaction

The Zimmerman-Traxler Model

The Acid-Catalyzed Aldol Condensation

The Reformatsky Reaction

Tsuji-Trost Reaction

Tebbe and Petasis Reactions