ULTIMATE GUIDE TO CHEMICAL REACTIONS IN ORGANIC CHEMISTRY (ALDEHYDES

AND KETONES):

Reaction Reaction Reaction Products Formed Reagents Used

Intermediates Mechanism
Hydrate Gem-diol Nucleophilic Gem-diol Water (H₂O)
Formation addition of water
Cyanohydrin Cyanohydrin Nucleophilic Cyanohydrin HCN
Formation addition of
cyanide
Reduction of Alkoxide Nucleophilic Primary alcohol NaBH₄
Aldehydes intermediate addition of hydride
(NaBH₄) ion
Reduction of Alkoxide Nucleophilic Primary alcohol LiAlH₄
Aldehydes intermediate addition of hydride
(LiAlH₄) ion
Reduction of Alkoxide Nucleophilic Secondary alcohol NaBH₄
Ketones (NaBH₄) intermediate addition of hydride
ion
Reduction of Alkoxide Nucleophilic Secondary alcohol LiAlH₄
Ketones (LiAlH₄) intermediate addition of hydride
ion
Grignard Addition Alkoxide Nucleophilic Primary alcohol Grignard reagent
to Aldehydes intermediate addition of and aldehyde
Grignard reagent
Grignard Addition Alkoxide Nucleophilic Secondary alcohol Grignard reagent
to Ketones intermediate addition of and ketone
Grignard reagent
Acetal Formation Hemiacetal Nucleophilic Acetal Alcohol, acid
intermediate addition of catalyst
alcohol, f ollowed
by acid-catalyzed
dehydration
Acetal Hydrolysis Hemiacetal Acid-catalyzed Aldehyde/ketone Acid (H₃O⁺)
intermediate hydrolysis of and alcohol
acetal
Imine Formation Imine intermediate Nucleophilic Imine and water Amine
addition of amine,
 f ollowed by
dehydration
Enamine Enamine Nucleophilic Enamine and Secondary amine,
Formation intermediate addition of water acid catalyst
secondary amine,
f ollowed by
dehydration
Wolf f -Kishner Hydrazone Reduction of Alkane and N₂ Hydrazine (N₂H₄),
Reduction intermediate hydrazone to KOH, heat
alkane
Clemmensen Carbocation Reduction of Alkane Zn(Hg), HCl
Reduction intermediate ketone to alkane
using zinc
amalgam and HCl
Oxidation to Carboxylic acid Oxidation of Carboxylic acid Oxidizing agents
Carboxylic Acid aldehyde or (e.g., H₂CrO₄,
ketone KMnO₄)
Keto-Enol Enol Acid-base Keto and enol Acid or base
Tautomerism catalyzed tautomers catalyst
interconversion
between keto and
enol f orms
Enolate Formation Enolate ion Deprotonation of Enolate ion Strong base (e.g.,
alpha-carbon by LDA, NaOEt)
strong base
Aldol Addition β-Hydroxy Nucleophilic β-Hydroxy Base catalyst
Reaction carbonyl addition of enolate carbonyl
compound to carbonyl compound
Alkylation of Alkylated carbonyl Nucleophilic Alkylated carbonyl Enolate and alkyl
Enolates compound substitution of compound halide
alkyl halide with
enolate
Wittig Reaction Alkene Formation of Alkene and Phosphonium
alkene via phosphine oxide ylide and
phosphonium aldehyde/ketone
ylide intermediate
Thioacetal Thioacetal Nucleophilic Thioacetal Thiol, acid catalyst
Formation addition of thiol,
f ollowed by acid-
catalyzed
dehydration
Imine Hydrolysis Imine intermediate Hydrolysis of Aldehyde/ketone Acid or base
imine to and amine
regenerate
carbonyl
compound
Oxidation to Silver mirror Oxidation of Carboxylic acid Tollens' reagent
Carboxylic Acids aldehyde to and silver mirror (Ag₂O, NH₃)
(Tollens') carboxylic acid
using silver(I)
oxide
Halof orm Halof orm Halogenation of Carboxylic acid Halogen (Cl₂, Br₂,
Reaction intermediate methyl ketone, and halof orm I₂) and base
f ollowed by base-
catalyzed
cleavage
Baeyer-Villiger Peroxyacid Oxidation of Ester Peroxyacid (e.g.,
Reaction intermediate ketone to ester m-CPBA)
Aldol β-Unsaturated Aldol addition β-Unsaturated Base catalyst
Condensation carbonyl f ollowed by carbonyl
compound dehydration compound and
water
Cannizzaro Carboxylic acid Disproportionation Carboxylic acid Strong base (e.g.,
Reaction and alcohol of aldehydes and alcohol NaOH)
without alpha-
hydrogens
Organolithium Alkoxide Nucleophilic Primary alcohol Organolithium
Addition to intermediate addition of reagent and
Aldehydes organolithium aldehyde
reagent
Ketone α-Halo ketone Acid-catalyzed α-Halo ketone and Halogen (Cl₂, Br₂,
Halogenation halogenation at HX I₂) and acid
alpha-carbon

Notes:

• Nucleophilic addition is a common reaction mechanism for aldehydes and ketones.

• Enolates are reactive intermediates formed by deprotonation of the alpha-carbon.
• Many reactions of aldehydes and ketones involve oxidation or reduction.
• Some reactions require specific conditions or reagents to proceed selectively.