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 cyanide
Mechanism
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J. Smith, Organic Chemistry, 2016, McGraw Hill.
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
Methods to obtain 1,2-diols
✓ Epoxidation of alkenes, then ring opening with acid
(backside attack)
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REACTIONS OF ALDEHYDE/KETONE
Protection of “C=O” functionality
Methods to obtain 1,2-diols
✓ Syn-dihydroxylation
of alkenes with
OsO4/KHSO3.
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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 21
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
INERT with NaBH4.
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REACTIONS OF ALDEHYDE/KETONE
Reduction
Hydrogenation with transition metals is not selective
at all!!!
can not stop!
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REACTIONS OF ALDEHYDE/KETONE
Reduction
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REACTIONS OF ALDEHYDE/KETONE
Oxidation
oxidation
reduction 28
REACTIONS OF ALDEHYDE/KETONE
Oxidation of aldehydes
Use of Cr(VI) compounds oxidizes aldehydes to acids.
KETONES ARE INERT IN OXIDATION! 29
REACTIONS OF ALDEHYDE/KETONE
Reaction of Cα to carbonyl
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.
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SYNTHESIS OF ALDEHYDE/KETONE
Ozonolysis
Mechanism
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SYNTHESIS OF ALDEHYDE/KETONE
Ozonolysis
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SYNTHESIS OF ALDEHYDE/KETONE
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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SYNTHESIS OF ALDEHYDE/KETONE
Friedel-Crafts acylation (for aromatic carbonyls)
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