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Aldol Addition Reactions: Based On Organic Chemistry, T.W. GRAHAM SOLOMONS and CRAIG B. FRYHLE 10e

Aldol addition reactions involve the addition of an enolate to a carbonyl compound. With ketones, the equilibrium favors the reactants due to steric hindrance. However, dehydration of the aldol product drives the reaction forward by forming a stable conjugated system. Retro-aldol reactions can also occur, converting β-hydroxy carbonyl compounds back to the original reactants. Crossed aldol condensations using different carbonyl compounds may produce multiple products and require specific conditions to favor one product over others.

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59 views11 pages

Aldol Addition Reactions: Based On Organic Chemistry, T.W. GRAHAM SOLOMONS and CRAIG B. FRYHLE 10e

Aldol addition reactions involve the addition of an enolate to a carbonyl compound. With ketones, the equilibrium favors the reactants due to steric hindrance. However, dehydration of the aldol product drives the reaction forward by forming a stable conjugated system. Retro-aldol reactions can also occur, converting β-hydroxy carbonyl compounds back to the original reactants. Crossed aldol condensations using different carbonyl compounds may produce multiple products and require specific conditions to favor one product over others.

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N Aini
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Aldol Addition Reactions

Based on Organic Chemistry, T.W. GRAHAM SOLOMONS and CRAIG B. FRYHLE 10e
Aldol Addition Reactions
An aldol addition is an equilibrium reaction when it is conducted in a protic solvent with
a base such as hydroxide or an alkoxide.
The Retro-Aldol Reaction

With ketones, the addition step leading to the aldol is unfavorable due to steric hindrance,
and the equilibrium favors the aldol precursors rather than the addition product.

However, dehydration of the aldol addition product can draw the equilibrium toward
completion, whether the reactant is an aldehyde or a ketone. Enolate additions to both
aldehydes and ketones are also feasible when a stronger base (such as LDA) is used in an
aprotic solvent.

Because the steps in an aldol addition mechanism are readily reversible, a retro-aldol
reaction can occur that converts a β-hydroxy aldehyde or ketone back to the precursors of
an aldol addition.
Aldol Condensation Reactions: Dehydration of the
Aldol Addition Product

The stability of the conjugated enal or enone system means that the dehydration
equilibrium is essentially irreversible.

Even though hydroxide is a leaving group in this reaction, the fact that each dehydrated
molecule forms irreversibly, due to the stability from conjugation, draws the reaction
forward.
Acid-Catalyzed Aldol Condensations
Synthetic Applications of Aldol Reactions
Crossed Aldol Condensations
An aldol reaction that starts with two different carbonyl compounds is called a
crossed aldol reaction. Unless specific conditions are involved, a crossed aldol
reaction can lead to a mixture of products from various pairings of the carbonyl
reactants.
Crossed Aldol Condensations Using Weak Bases
Crossed Aldol Condensations Using Strong Bases:
Lithium Enolates and Directed Aldol Reactions
Cyclizations via Aldol Condensations

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