ALDEHYDE-KETONE

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 REACTIONS OF ALDEHYDE/KETONE
Nucleophilic addition (AN)
The most typical reaction of aldehyde/ketone is
nucleophilic addition

Reactivity

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 REACTIONS OF ALDEHYDE/KETONE
Addition of Grignard reagents

Step 1

Step 2

H2O is OK
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 REACTIONS OF ALDEHYDE/KETONE
Addition of Grignard reagents
Reactions with formaldehyde affords primary alcohols.

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 REACTIONS OF ALDEHYDE/KETONE
Addition of Grignard reagents
Reactions with other aldehydes afford secondary alcohols, with
ketones afford tertiary alcohols.

2nd alcohol

3rd alcohol
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 REACTIONS OF ALDEHYDE/KETONE
Addition of acetylides
Sodium acetylides (via deprotonation of terminal alkynes with
NaNH2) react with aldehydes/ketones to afford alcohols.

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 REACTIONS OF ALDEHYDE/KETONE
Addition of amines
Reactions of primary amines afford imines.

Example

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 REACTIONS OF ALDEHYDE/KETONE
Addition of amines
Mechanism

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 REACTIONS OF ALDEHYDE/KETONE
Addition of amines
Reactions of secondary amines afford enamines.

Example

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 REACTIONS OF ALDEHYDE/KETONE
Addition of amines
Mechanism

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 REACTIONS OF ALDEHYDE/KETONE
Addition of amines
Reactions of aldehydes or ketones with hydrazine afford
hydrazones, which are “decomposed” into alkanes in the
presence of strong base.

Wolff-Kishner reduction

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 REACTIONS OF ALDEHYDE/KETONE
Wolff-Kishner reduction
Mechanism

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 REACTIONS OF ALDEHYDE/KETONE
Addition of water

Examples

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 REACTIONS OF ALDEHYDE/KETONE
Addition of alcohols

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 REACTIONS OF ALDEHYDE/KETONE
Addition of alcohols
Mechanism

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 REACTIONS OF ALDEHYDE/KETONE
Protection of “C=O” functionality
Reactions of aldehydes or ketones with diols would form
cyclic acetals or ketals, as protecting groups for “C=O”.

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 REACTIONS OF ALDEHYDE/KETONE
Protection of “C=O” functionality
Protecting groups are important in selective reductions.

Ketone is protected
Bronsted acid catalyst
from reduction

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 REACTIONS OF ALDEHYDE/KETONE
Wittig reaction
Reactions of aldehydes or ketones with phosphonium ylides
afford alkenes.

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 REACTIONS OF ALDEHYDE/KETONE
Wittig reaction
Mechanism

Reaction of ylide is
similar to that of
Grignard reagent 19
 REACTIONS OF ALDEHYDE/KETONE
Reduction
Use of H2 in the presence of transition metals (Ni,
Pd, Pt) reduces aldehydes/ketones to alcohols.

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 REACTIONS OF ALDEHYDE/KETONE
Reduction
Use of NaBH4 or LiAlH4 reduce aldehydes or ketones
to alcohols.

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 REACTIONS OF ALDEHYDE/KETONE
Reduction
Use of NaBH4 or LiAlH4 reduce aldehydes or ketones
to alcohols.

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 REACTIONS OF ALDEHYDE/KETONE
Reduction
NaBH4 is much more selective than LiAlH4.

Unsaturated C–C bonds (in alkenes, alkynes) are

can not stop!

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 REACTIONS OF ALDEHYDE/KETONE
Reduction

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 REACTIONS OF ALDEHYDE/KETONE
Oxidation
oxidation

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reduction
 REACTIONS OF ALDEHYDE/KETONE
Oxidation of aldehydes
Use of Cr(VI) compounds oxidizes aldehydes to acids.

KETONES ARE INERT IN OXIDATION! 27

E is an electrophile

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 REACTIONS OF ALDEHYDE/KETONE
Reaction of Cα to carbonyl
Cα to carbonyl is able to react with another carbonyl
to obtain β-hydroxy ketone.

Aldol addition

Example

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 REACTIONS OF ALDEHYDE/KETONE
Reaction of Cα to carbonyl
Aldol additions

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 REACTIONS OF ALDEHYDE/KETONE
Aldol addition
Mechanism

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 REACTIONS OF ALDEHYDE/KETONE
Aldol condensation (dehydration of aldol product)
If heating is applied, dehydration may occur to form a
conjugated product.

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 REACTIONS OF ALDEHYDE/KETONE
Aldol condensation (dehydration of aldol product)
“Long” conjugation sometimes favors the aldol
condensation without heating.

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 REACTIONS OF ALDEHYDE/KETONE
Cross aldol addition

Two different carbonyl compounds are used.

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 REACTIONS OF ALDEHYDE/KETONE
Intramolecular aldol addition

Five- or six-membered ring is favored.

Mechanism

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 SYNTHESIS OF ALDEHYDE/KETONE
Ozonolysis

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 SYNTHESIS OF ALDEHYDE/KETONE
Ozonolysis

Aromatic is INERT with ozonolysis

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 SYNTHESIS OF ALDEHYDE/KETONE
“Hydration” of alkynes

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 SYNTHESIS OF ALDEHYDE/KETONE
Oxidation of alcohols
Use of PCC oxidizes primary alcohols to aldehydes,
secondary alcohols to ketones.

Tertiary alcohols are not oxidizable!

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