Organic Chemistry Reaction Table x6b44

Alkene Rxns Hydrohalogenation Hydration Hydration (with rearrangement) Addition of Alcohol Bromination Bromination in H2O

Bromination in Alcohol

OxymercurationDemurcuration AlkoxymercurationDemurcuration HydroborationOxidation Catalytic Hydrogenation (Catalytic Reduction) Hydrobromination with Peroxide Epoxidation Anti-Hydroxylation Syn-Hydroxylation Syn-Hydroxylation Ozonolysis under Reducing Conditions

1

Ozonolysis under Oxidizing Conditions Oxidative Cleavage

Free Radical Halogenation Free Radical Bromination (high selectivity) Free Radical Chlorination (low selectivity) Allylic/Benzylic Bromination

Grignard Rxns Nucleophilic Addition of a Grignard Reagent to a Ketone

Nucleophilic Addition of a Grignard Reagent to an Epoxide (attacks less substituted side) Nucleophilic Addition of a Grignard Reagent to CO2 Protonation of a Grignard Reagent (Grignards are protonated in protic solutions)

2

Alkyne Rxns Catalytic Hydrogenation (Catalytic Reduction) Reduction to cis-alkene Reduction to trans-alkene Hydrohalogenation

Hydration of an Internal Alkyne

Hydration (Markovnikov) Hydration (Anti-Markovnikov) SN2 Addition of an Acetylide Ion Addition of an Acetylide Ion to a Ketone

O NaNH2

1.

HO

2. H2O

Addition of an Acetylide Ion to an Epoxide

3

Benzene Rxns Nitration (EAS) Sulfonation (EAS) Chlorination (EAS) Bromination (EAS) Friedel-Crafts Alkylation (EAS)

Cl AlCl3

Friedel-Crafts Alkylation (EAS) (with rearrangement) Friedel-Crafts Acylation (EAS)

Bromination (EAS) -NH2 is an ortho/para director and doesn’t require a catalyst like FeBr3 Chlorination (EAS) -OH is an ortho/para director

OH

OH Cl2 AlCl3

OH Cl

+ Cl

Chlorination (EAS) -OR is an ortho/para director

Chlorination (EAS) -CH3 is an ortho/para director

Chlorination (EAS) -Br is an ortho/para director

4

Chlorination (EAS) Carbonyl is a meta director

Chlorination (EAS)

NO2

Cl2

NO2

AlCl3

-NO2 is a meta director

Cl

Chlorination (EAS) -CN is a meta director Chlorination (EAS) -SO3H is a meta director Chlorination (EAS) -CF3 is a meta director Clemmensen Reduction

O

Zn (Hg) HCl Wolff-Kishner Reduction

Side-chain Oxidation (Benzylic Oxidation)

Side-chain Oxidation (Benzylic Oxidation)

5

Alcohol Rxns Conversion to an alkyl iodide Conversion to an alkyl bromide Conversion to an alkyl chloride Conversion to an alkyl chloride with thionyl chloride (only for 1 and 2 ) Conversion to an alkyl bromide (only for 1 and 2 ) Conversion to a tosylate ester Acid-catalyzed Dehydration Chromic Acid Oxidation of a 1 Alcohol (Chromic Acid can also be written as H2CrO4 or CrO3/H2SO4) 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

Ether Rxns Williamson Ether Synthesis (2nd step is SN2) Acid-Catalyzed cleavage of Ethers (also works with HI and HCl)

Epoxide Rxns Base-Catalyzed Ring Opening of an Epoxide (Attacks less-substituted side) Acid-Catalyzed Ring Opening of an Epoxide (Attacks more-substituted side) 6

Hydride Reduction Rxns Reduction of a ketone to a 2 alcohol

Reduction of a aldehyde to a 1 alcohol

Reduction of an acid chloride to a 1 alcohol O

1. LiAlH4 Cl

2. H3O+

OH

Reduction of an ester to two alcohols Reduction of a carboxylic acid to a 1 alcohol Reduction of an amide to an amine Reduction of an ester to an aldehyde using DIBALH (also called DIBAH) DIBALH is diisobutylaluminum hydride (shown below)

Reduction of an acid chloride to an aldehyde using tri-tbutoxyaluminum hydride Hoffman Rearrangment Converts an amide to an amine with the loss of a carbon (note the difference with reduction of an amide with LiAlH4 where there is no loss of carbon)

7

Carboxylic Acids and Derivatives (Nucleophilic Acyl Substitution

Diels-Alder Rxns Basic Diels-Alder Rxn (a 4+2 cycloaddition rxn)

8

Nucleophilic Addition to Ketones and Aldehydes Addition of water to form a hydrate

Addition of an alcohol under basic conditions to form a hemiketal

Addition of 1eq of an alcohol in acid to form a hemi-ketal and then a 2nd eq to form a ketal

Addition of ethylene glycol to from a cyclic ketal which functions as a protecting group for ketones and aldehydes H3O+ is used to de-protect Addition of a 1 amine to form an imine

R

O

N

RNH2

(can be reversed with H3O+)

H2O

H+

H3O+ Addition of a 2 amine to form an enamine Forms on less substituted side if there’s a difference (can be reversed with H3O+)

R

O R2NH H+

N

R H2O

H3O+

9

Wittig Rxn Addition of a phosphylide to form an alkene

Michael Addition with a lithium dialkylcuprate

R2

PPh3 R2

R1 Formation of a phosphoylide from an alkyl halide Michael Addition (also called -addition or conjugate addition)

R1

R1

O

Br

PPh3

R1 PPh3 R2

R2

BuLi acts as a base

R1 PPh3 R2

O

O (CH3)2CuLi H2O

CH3

10

Alpha Addition Rxns Self Aldol Condensation

Mixed Aldol Condensation O

O

OH-

H

O

O

OH H

H

Self Claisen Condensation

Mixed Claisen Condensation

O

1. LDA

O

O

O

2.

OEt 3. H2O Malonic Ester Synthesis

Acetoacetic Ester Synthesis O EtO

O

1. NaOEt 2.

Br

O O EtO

O +

H3O

CO2

3. NaOEt 4.

Br

11