ORGANIC CHEMISTRY COMPLETE SUMMARY OF REACTIONS

SUMMARY OF SUBSTITUTION AND ELIMINATION REACTIONS

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 SUMMARY OF REACTIONS OF ALKENES
Reagents 2 Groups Regioselectivity Stereo- Intermediate Rearrange-
Added specificity ments
Hydrohalogenation
HX (X = halogen) H and X Markovnikov none carbocation Possible

HBr/ROOR H and Br Anti-Markovnikov none radicals No

Hydration
H3O+ (i.e. dil. H2SO4) H and OH Markovnikov none carbocation Possible

1. Hg(OAc)2, H2O H and OH Markovnikov Anti mercurinium No

2. NaBH4 ion

1. BH3.THF H and OH Anti-Markovnikov Syn trialkyl No

2. H2O2, NaOH borane
Alcohol Addition
ROH, H+ (usually H2SO4) H and OR Markovnikov none carbocation Possible

1. Hg(OAc)2, ROH H and OR Markovnikov Syn mercurinium No

2. NaBH4 ion
Catalytic Hydrogenation
H2/catalyst H and H N/A Syn - No
(Catalyst = Pt, Pd, or Ni)
Halogenation
X2/inert solvent X and X N/A Anti halonium ion No

X = Br, Cl
inert solvents = CCl4, CH2Cl2

Halohydrin Formation
X2/H2O X and OH Markovnikov Anti halonium ion No

X2/ROH X and OR Markovnikov Anti halonium ion No

Dihydroxylation
1. RCO3H (usually MCPBA) OH and OH N/A Anti epoxide No
2. H3O+

1. OsO4 OH and OH N/A Syn cyclic osmate No

2. NaHSO3 or Na2SO3 ester

KMnO4 (cold, dilute)/NaOH OH and OH N/A Syn cyclic No

manganate
ester

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 SUMMARY OF REACTIONS OF ALKENES
Hydrohalogenation

Hydrobromination with Peroxide

Acid-Catalyzed Hydration

Acid-Catalyzed Hydration
(with rearrangement)
Oxymercuration-Demercuration

Hydroboration-Oxidation

Acid-Catalyzed Addition of an
Alcohol
Alkoxymercuration-Demercuration

Catalytic Hydrogenation
(Catalytic Reduction)

Halogenation

Halohydrin Formation

Epoxidation

Anti-Hydroxylation

Syn-dihydroxylation

Syn-dihydroxylation

Ozonolysis
(Under Reducing Conditions)
Ozonolysis
(Under Oxidizing Conditions)

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 SUMMARY OF ALKYNE SYNTHESIS
Elimination of a Geminal Dihalide

Elimination of a Geminal Dihalide

Elimination of a Vicinal Dihalide

SUMMARY OF REACTIONS OF ALKYNES

Reduction (Addition of Hydrogen)

Hydrohalogenation
(HCl, HBr, HI)

Hydrobromination with Peroxide

Halogenation (Br2 or Cl2)

Acid-Catalyzed Hydration
of a Terminal Alkyne
Hydroboration-Oxidation
of a Terminal Alkyne
Hydration of an Internal Alkyne

Ozonolysis of an Internal Alkyne

Ozonolysis of a Terminal Alkyne

Alkylation of Acetylide Ions

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 SUMMARY OF FREE RADICAL HALOGENATIONS
Free Radical Bromination
(high selectivity)
Free Radical Chlorination
(low selectivity)
Allylic / Benzylic Bromination

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 SUMMARY OF ALCOHOL SYNTHESIS
SN2
SN1

Acid-Catalyzed Hydration

Oxymercuration-
Demercuration

Hydroboration-Oxidation

Anti-Hydroxylation

Syn-Hydroxylation

Reduction of Ketones

Reduction of Aldehydes

Grignard Addition to
Ketones and Aldehydes

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 SUMMARY OF REACTIONS OF ALCOHOLS
Substitution with Iodide

Substitution with Bromide

Substitution with Chloride

Substitution with Bromide

(only for 1 and 2)
Substitution with Chloride
(only for 1 and 2)
Conversion to a tosylate ester
(a good leaving group)
Acid-catalyzed Dehydration
(Zaitsev product is major)

Chromic Acid Oxidation of a 1 Alcohol

PCC Oxidation of a 1 Alcohol

Chromic Acid Oxidation of an Aldehyde

Chromic Acid Oxidation of a 2 Alcohol

PCC Oxidation of a 2 Alcohol

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 SUMMARY OF SYNTHESIS / REACTIONS OF ETHERS
Williamson Ether Synthesis
(2nd step is SN2)
Acid-Catalyzed cleavage of Ethers
(also works with HI and HCl)
Acid-Catalyzed cleavage of Phenyl Ethers

SUMMARY OF SYNTHESIS / REACTIONS OF EPOXIDES

SN2

Epoxidation with a Peroxyacid

Sharpless Epoxidation

Base-Catalyzed Ring Opening of an Epoxide

(Attacks less substituted side)

Acid-Catalyzed Ring Opening of an Epoxide

(Attacks more substituted side usually)

SUMMARY OF SYNTHESIS / REACTIONS OF THIOLS AND SULFIDES

Thiol Synthesis via SN2
Oxidation (Disulfide Formation)

Sulfide Synthesis via SN2

Oxidation of Sulfides

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 SUMMARY OF REACTIONS OF AROMATIC COMPOUNDS
Bromination

Chlorination

Sulfonation

Desulfonation
Nitration

Friedel-Crafts Alkylation

Friedel-Crafts Acylation

Formylation
(Gattermann-Koch Synthesis)

Catalytic Hydrogenation

Birch reduction

Side-chain Oxidation
(Benzylic Oxidation)

Side-chain Oxidation
(Benzylic Oxidation)

Clemmensen Reduction

Wolff Kishner Reduction

General Reduction

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 SUMMARY OF SYNTHESIS OF KETONES AND ALDEHYDES
Oxidation of a 1 Alcohol with PCC

Oxidation of a 2 Alcohol with PCC

Oxidation of a 2 Alcohol with Chromic Acid

Ozonolysis Under Reducing Conditions

Hydration of a Terminal Alkyne (Markovnikov)

Hydration of a Terminal Alkyne (Anti-

Markovnikov)
Hydration of an Internal Alkyne

Friedel-Crafts Acylation

Formylation (Gatterman-Koch Synthesis)

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 SUMMARY OF REACTIONS OF KETONES AND ALDEHYDES
Addition of Water
(Hydrate Formation)

Addition of Alcohols
(Hemiacetal Formation)
or
(Acetal Formation)

Addition of Ethylene Glycol

(as a Protecting Group)

Reversible with H3O+

Addition of a 1 amine
(Imine Formation)

Reversible with H3O+

Addition of a 2 amine
(Enamine Formation)

Reversible with H3O+

Reduction via Thioacetals
(also accomplished by
Clemmensen and Wolf Kishner
Reductions)
Hydride Reduction

Addition of Acetylide Ions

Addition of Grignard Reagents

Addition of HCN
(Cyanohydrin Formation)
Wittig

Baeyer-Villiger Oxidation

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 SUMMARY OF HYDRIDE REDUCTION REACTIONS
Sodium Borohydride
(NaBH4)

Lithium Aluminum Hydride

(LiAlH4 or LAH)

Lithium Tri-t-butoxy
Aluminum Hydride

Diisobutyl Aluminum Hydride

(DIBAH or DIBALH)

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 SUMMARY OF REACTIONS OF ORGANOMETALLICS
Grignard Reagents

Lithium Dialkyl Cuprates

(Gilman Reagents)

SUMMARY OF INTERCONVERSION OF CARBOXYLIC ACIDS / DERIVATIVES

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 SUMMARY OF SYNTHESIS OF ACID HALIDES
Substitution with SOCl2 / PBr3

SUMMARY OF REACTIONS OF ACID CHLORIDES

Reaction with Organometallics

Hydride Reduction

Interconversion of Carboxylic Acids

and Acid Derivatives

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 SUMMARY OF SYNTHESIS OF ACID ANHYDRIDES
Interconversion of Carboxylic Acid
Derivatives

SUMMARY OF REACTIONS OF ACID ANHYDRIDES

Reaction with Organometallics

Hydride Reduction

Interconversion of Carboxylic Acids

and Acid Derivatives

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 SUMMARY OF SYNTHESIS OF ESTERS
Baeyer-Villiger Oxidation of
Ketones
Interconversion of Carboxylic Acid
Derivatives

Fischer Esterification

Trans-Esterification

SN2 with Carboxylates

SUMMARY OF REACTIONS OF ESTERS

Reaction with Organometallics

Hydride Reduction

Interconversion of Carboxylic Acids

and Acid Derivatives

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 SUMMARY OF SYNTHESIS OF CARBOXYLIC ACIDS
Ozonolysis of Alkenes under
Oxidizing Conditions
Ozonolysis of Alkynes

Chromic Acid Oxidation of 1

Alcohols and Aldehydes

Side-Chain Oxidation of Benzenes

Baeyer-Villiger Oxidation of
Aldehydes
Hydrolysis of Nitriles

Grignard Addition to CO2

SUMMARY OF REACTIONS OF CARBOXYLIC ACIDS

Reduction

Interconversion of Carboxylic Acids

and Acid Derivatives

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 SUMMARY OF SYNTHESIS OF AMIDES
Interconversion of Carboxylic Acid
Derivatives

SUMMARY OF REACTIONS OF AMIDES

Hydride Reduction

Interconversion of Carboxylic Acids

and Acid Derivatives
Dehydration

Hofmann Rearrangement

SUMMARY OF SYNTHESIS OF NITRILES

SN2

Dehydration of an Amide

SUMMARY OF REACTIONS OF NITRILES

Hydride Reduction

Grignard Addition

Hydrolysis

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 SUMMARY OF SUBSTITUTION REACTIONS AT THE ALPHA CARBON
Alpha Halogenation

HVZ Reaction

Alpha Alkylation

Stork Reaction
(Alternative for alpha
alkylation)

Self Aldol Reaction

Mixed Aldol Reaction

Intramolecular Aldol
Reaction

Self Claisen Condensation

Mixed Claisen
Condensation

Intramolecular Claisen
Condensation
(Dieckmann
Condensation)
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Malonic Ester Synthesis

Acetoacetic Ester
Synthesis

Michael Addition
(Conjugate Addition)

Robinson Annulation
1) Michael Addition
2) Intramolecular Aldol

SUMMARY OF AMINE REACTIONS

Hofmann Rearrangement

Curtius Rearrangement

Schmidt Reaction

Gabriel Synthesis

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Reductive Amination

Acylation

Hofmann Elimination

Cope Elimination

Sandmeyer Reactions
(of Arenediazonium Salts)

EAS with Heterocycles

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