Condensed Reaction Summary Sheet PDF

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Reaction Summary SheetAlkene Reactions (Sections 6–6, 6)HydrohalogenationHydrohalogenation (with Rearrangement)HydrationHydration (with Rearrangement)Oxymercuration- DemurcurationAlkoxymercuration- DemurcurationAddition of an AlcoholHalogenationBromination in H 2 OBromination in AlcoholHydroboration...

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Reaction Summary Sheet Alkene Reactions (Sections 6.1–6.8, 6.11) Hydrohalogenation

Hydrohalogenation (with Rearrangement) Hydration Hydration (with Rearrangement) OxymercurationDemurcuration

AlkoxymercurationDemurcuration Addition of an Alcohol

Halogenation

Bromination in H 2O

Bromination in Alcohol

HydroborationOxidation Hydrobromination with Peroxide Epoxidation

Anti-Dihydroxylation

Syn-Dihydroxylation

Syn-Dihydroxylation

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Ozonolysis (Reducing Conditions)

Ozonolysis (Oxidizing Conditions)/Oxidative Cleavage

HO

OH

O

HIO4

O H

H

Oxidative Cleavage of a 1,2 Diol

HO

OH

HIO4

O

O H

“Ozonolysis” with OsO4 and HIO4

Catalytic Hydrogenation *Pt can also be used* Thermodynamic vs. Kinetic products

Alkyne Reactions (Sections 6.7–6.10) Ozonolysis/Oxidative Cleavage on an Internal Alkyne

Ozonolysis/Oxidative Cleavage on a Terminal Alkyne Catalytic Hydrogenation (Catalytic Reduction) Reduction to Cis-Alkene

H2 Lindlar ’s Catalyst

Reduction to TransAlkene Hydrohalogenation with HBr (Terminal Alkyne) 2 of 17|Page

Hydrohalogenation with HBr (Internal Alkyne)

Halogenation with Br2

Halogenation with Br2 and peroxide Hydration of an Internal Alkyne Hydration of a Terminal Alkyne (Markovnikov) Hydration of a Terminal Alkyne (Anti-Markovnikov) SN2 Addition of an Acetylide Ion to an Alkyl Halide SN2 Addition of an Acetylide Ion to a Ketone SN2 Addition of an Acetylide Ion to an Epoxide

Alcohol Reactions (Sections 8.1–8.2) Conversion of a 2˚/3˚Alcohol to an alkyl halide via SN1

Conversion of a 1˚/2˚Alcohol to an alkyl bromide via SN2

OH

HX

X

OH

HX

X

OH

PBr3

H OH

H PBr3

OH Conversion of a 1˚/2˚Alcohol to an alkyl chloride via SN2

Conversion of an Alcohol to a Tosylate Ester (OTs)

SOCl2 Pyridine H

OH

OH

Br

SOCl2 Pyridine

TsCl

Br

Cl H Cl

OTs

Retention of Stereochemistry

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Acid-catalyzed Dehydration of an Alcohol Chromic Acid Oxidation of a 1o Alcohol to a Carboxylic Acid

OH

OH H

Chromic Acid Oxidation of a 2o Alcohol to a Ketone

OH

H3O+

Zaitsev’s Rule

Na2Cr2O7 or CrO3 H2SO4 Na2Cr2O7 or CrO3

O OH

O

H2SO4

Chromic Acid Oxidation of an Aldehyde to a Carboxylic Acid

Na2Cr2O7 or CrO3

O

H2SO4

H PCC or DMP Oxidation of a 1o Alcohol to an Aldehyde PCC or DMP Oxidation of a 2o Alcohol to a Ketone

OH

O OH O

PCC or DMP

H

OH

H

O

PCC or DMP

Oxidizing benzyl and allyl alcohols with MnO2

Baeyer-Villiger Oxidation

Ether Reactions (Section 8.3) Williamson Ether Synthesis via SN2

NaH, Na, or K

Cl

OH

O

O

HBr Acid-catalyzed Cleavage of Ethers when one side is 2˚/3˚ (Nucleophile attacks more substituted side via SN1)

O

HO

Br

HO

HBr O

Acid-catalyzed Cleavage of Ethers when neither side is 2˚/3˚ (Nucleophile attacks less substituted side via SN2)

Br

O

HBr

OH Br

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Epoxide Reactions (Section 8.4) Epoxidation

HCl

O

H3O+

O

OCH3 HOCH3

Acid-catalyzed Ring Opening of Epoxides (Nucleophile attacks more substituted side)

Base-catalyzed Ring Opening of Epoxides (Nucleophile attacks less substituted side)

O

Addition of a Grignard Reagent to an Epoxide (adds to the less subs. side)

Cl

O

1.

OH OH OH

OH O

OH

MgX , Ether

2. H3O+

Free Radical Halogenation Reactions (Section 10.3) Free Radical Halogenation using Bromine (more selective)

Br

Br2 hv or Δ Cl

Free Radical Halogenation using Chlorine (less selective)

Cl

Cl2

Cl

hv or Δ

Cl

Allylic/Benzylic Bromination

NBS hv or Δ or ROOR

Br

NBS hv or Δ or ROOR

Br Br

Diels-Alder Reactions (Section 10.3) Diene Addition to a Dienophile (Alkene)

hv or

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Diene Addition to a Dienophile (Alkyne)

hv or hv or

Diene Addition to a cis Dienophile same

hv or

Diene Addition to a trans Dienophile

enantiomers

H

O

H O Diene Addition to a substituted Dienophile

H

endo (Major) O

hv or

H H

O H

O exo (Minor)

H

H

Benzene Side-Chain Reactions (Section 11.3) R or

R

or

O

1. KMnO4, -OH 2. H3O+, Heat

R

OH

or Na2Cr2O7 H2SO4

Side-Chain Oxidation of Benzene to form Benzoic Acid

O Zn(Hg), HCl, Heat *can also use H2/Pd, C

Clemmensen Reduction

NO2

Zn(Hg), HCl, Heat

NH2 *can also use H 2/Pd, C or Sn/HCl

O Wolff-Kishner Reduction

H2NNH2 or N2H4, -OH, Heat

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NH2

Acetylation of Aniline using Acetic Anhydride

O

H N

O

O pyridine

Aniline

O Acetanilide

Electrophilic Aromatic Substitution (EAS) Reactions (Section 11.4) HNO3

Nitration

NO2

H2SO4

Sulfonation

Chlorination

Cl2 FeCl3

Bromination

Br2

Cl

Br

FeBr3 Cl AlCl3 Friedel-Crafts Alkylation (Rearrangement Possible)

Cl AlCl3 O

Friedel-Crafts Acylation (No Rearrangement Possible)

O

Cl AlCl3

O Formylation

CO, HCl

H

AlCl3 O/P EAS with an ortho/paradirecting group on Benzene

O/P Substituent

O/P Substituent

Substituent

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M

M

EAS with a meta-directing group on Benzene

Substituent Substituent

M Friedel-Crafts Alkylation/Acylation with a meta-directing group or an amine on Benzene

O R Cl

or Cl

R

No Reaction

AlCl3 NH2/NRH/NR2

O R Cl

or Cl

R

No Reaction

AlCl3

Diazonium Salt Reactions (Section 11.5)

NH2

N2 +

NaNO2, HCl (HONO)

F

4

F

KI

E or

Br or Cl

HB

+

Cu CN

l uC

O H3

B Cu

rC ro

H3PO2

tOH

CN

I

OH

Aldehyde and Ketone Reactions (Sections 12.1–12.2) Nucleophilic Addition to an Aldehyde or Ketone

O

Addition of water to an Aldehyde or Ketone forming a Hydrate

O

Base-catalyzed addition of an Alcohol to an Aldehyde or Ketone forming a Hemiacetal/Hemi-ketal

Nucleophile C or H

H2O C or H

O

O Acid-catalyzed addition of an Alcohol to an Aldehyde or Ketone forming a Acetal/Ketal (Protecting Group, reversed by H3O+)

C or H HO

OH C or H

HO

HO

O C or H

HO H3O+

C or H

Nucleophile

H3O+ or -OH O

C or H

HO

H3O+

O

O C or H

H3O+

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O Acid-catalyzed addition of Ethylene Glycol to an Aldehyde or Ketone forming a Acetal/Ketal (Protecting Group, reversed by H3O+)

OH

HO C or H

O

O C or H

H3O+ H3O+

O Addition of a 1˚ Amine to an Aldehyde or Ketone forming an Imine (Reversed by H3O+)

N

H2N H3O+

C or H

C or H

H3O+

N H H3O+

O C or H

Addition of a 2˚ Amine to an Aldehyde or Ketone forming an Enamine (Reversed by H3O+)

N C or H

H3O+ Double bond forms on more substituted end for Ketones

Hydride Reduction Reactions (Section 12.3) O

1. NaBH4 H

Reduction of an Aldehyde to a 1˚Alcohol

O

O Reduction of a Ketone to a 2˚Alcohol

2. H3O+

H

1. LiAlH4 H

OH

OH

2. H3O+

H

1. NaBH4

OH

2. H3O+ O

1. LiAlH4

OH

2. H3O+

Grignard and Organolithium Reactions with Aldehydes and Ketones (Section 12.4) Addition of a Grignard Reagent to an Aldehyde

Addition of a Grignard Reagent to a Ketone

The Wittig Reaction (Section 12.5) Addition of a Wittig Reagent to an Aldehyde or Ketone

O

PPh3 C or H

C or H

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Michael (1,4) Additions (Section 12.6) O

O O

O Michael Addition to an α,β-Unsaturated Ketone

or -CN, HNR2, HSR etc.

O O

O

Michael Addition to an α, β Unsaturated Ketone with a Gilman Reagent (Organocuprates)

O (CH3CH2CH2)2CuLi

Interconversion of Carboxylic Acid Derivatives (Section 13.1) SOCl2 O R

Cl

Acyl Chloride O

O R‘

O

R’ R O Acid Anhydride

OH or

O

O R‘

O R

Carboxylic Acid OR’

R’OH/H+ ea

t

R’OH or R’O-

OH

R

H3O+/Heat

O

H

3O +

/H

Ester

H3O+

H+

H+

O R2NH or R2N-

R

NR’2

Amide O R -OH

O

Carboxylate

Forming Carboxylic Acids by Reacting Grignards with CO2 (Section 13.2) O

Addition of a Grignard Reagent to CO2

MgX

1. CO2, Ether

OH

2. H3O+

Carboxylic Acid

Fischer Esterification and Saponification (Section 13.3) Fischer esterification = forward reaction; saponification/hydrolysis = reverse reaction Fischer Esterification and Saponification

O

O

H3O+/CH3CH2OH

or OH

Cl

O O

H3O+ 10 of 17|Page

Hydride Reductions of Carboxylic Acid Derivatives (Sections 13.4–13.6) Reduction of an Acyl Chloride to a 1˚Alcohol

O

1. LiAlH4 Cl

2. H3O+

OH H

Reduction of an Acid Anhydride to a 1˚Alcohol

Reduction of an Ester to a 1˚Alcohol

Reduction of a Carboxylic Acid to a 1˚Alcohol

O

1. LiAlH4 O

2.

O

H3O+

1. LiAlH4

O

OH H

1. LiAlH4 NH2

NH2 2. H3O+

O

1. Br2

Hofmann Rearrangement

NH2 Reduction of an Ester to an Aldehyde

OH H

OH 2. H3O+

Reduction of an Amide to an Amine

OH

O

NH2

2. NaOH

O

1. DIBAL-H, -78°C O

H

2. H2O

Reduction of an Acyl Chloride to an Aldehyde

Reduction of a Nitrile to an Amine

N

1. LiAlH4 NH2

2. H3O+

Grignard Reactions with Carboxylic Acid Derivatives (Sections 13.6) Addition of a Grignard Reagent to an Ester

O

Addition of a Grignard Reagent to an Acyl Chloride

O

1. 2 eq. O

Addition of a Grignard Reagent to a Carboxylic Acid

HO

3˚Alcohol

2. H3O+

1. 2 eq. Cl

O

MgX, Ether

MgX, Ether

HO 3˚Alcohol

2. H3O+

1.

MgX, Ether

OH 2. H O+ 3 Carboxylate

O O

MgX

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O Addition of a Grignard Reagent to an Amide

O

MgX, Ether

1.

NH MgX

NH2 2. H O+ 3 Deprotonated Amide

Addition of a Grignard Reagent to a Nitrile

1.

N

O

MgX, Ether

Ketone

2. H3O+

Nitrile Reactions (Section 13.6) Acid-catalyzed Hydrolysis of a Nitrile

O

H3O+, Heat

C N

OH SN2 formation of Nitriles using Cyanide and Alkyl Halides

C N X

C

O

Cyanohydrin Formation using Aldehydes/Ketones and Cyanide

HO

C N

N N

C

C or H

C or H

Alpha-Substitution Reactions (Chapter 14) O

Alpha Halogenation in Acidic Conditions

O

Self-Aldol Condensation and Enone Formation

X X

X

X

O

X2 (excess) NaOH

R or H

X

X X

O

1. Acid (TFA) 2. X2

O Haloform Reaction

O

1. NaOH 2. X2 (excess)

Alpha Halogenation In Basic Conditions

R or H

CHX3

O

*A methyl group is required for this reaction O O OH -OH, H O H3O+, NaOH 2 2 H H Δ

O

-OH,

O

H2O

OH H3O+, NaOH

2 O

O

O

-

OH, H2O

Δ OH

H Mixed-Aldol Condensation and Enone Formation

O

O H

O

H3O+, NaOH

O

Δ

O

O -OH,

O H3O+, NaOH

H 2O

Δ HO 12 of 17|Page

Self-Claisen Condensation

Mixed-Claisen Condensation

O 2

O

1. O O

O

O 1. O 2. Cl 3. O 4. Cl 5. H3O+, Δ

O

O

CO2

HO

O

O 1.

O

O

2. H3O+

O

Acetoacetic Ester Synthesis

Malonic Ester Synthesis

O

1. O O

O

O

2. H3O+

O

O

O

O

CO2

HO

2. Cl 3. O 4. Cl 5. H3O+, Δ

2 HO

Intramolecular Aldol (Diketone) Condensations

Dieckmann Cyclization (Intramolecular Claisen Condensation)

O

O

O 1. O

O

O

2. H3O+

O O

The Robinson Annulation

Coupling Reactions (Chapter 15) Addition of a Grignard Reagent to an Epoxide (adds to the less subs. side)

O

1.

MgX, Ether

OH

2. H3O+

The Gilman Reaction

The Suzuki Reaction

The Heck Reaction The Stille Reaction 13 of 17|Page

Olefin Metathesis

Amine Reactions (Chapter 16) Reductive Amination

Hydrogenating Alkyl Azides Hydrogenating Nitriles

Gabriel Synthesis

NAS (Nucleophilic Aromatic Substitution) Reactions with –NH2

Adding Cyanide to Aldehydes & Ketones Acid-catalyzed Hydrolysis of a Nitrile

O

H3O+, Heat

C N

OH

The Hofmann Elimination

Acid Chlorides + Amines Addition of a 1˚ Amine to an Aldehyde or Ketone forming an Imine (Reversed by H3O+)

O C or H

H3O+

C or H

H3O+

O Addition of a 2˚ Amine to an Aldehyde or Ketone forming an Enamine (Reversed by H3O+)

N

H2N

C or H

N H H3O+

N C or H

H3O+ Double bond forms on more substituted end for Ketones 14 of 17|Page

Reducing Nitro Groups

O Reduction of an Amide to an Amine Reduction of a Nitrile to an Amine

1. LiAlH4 NH2

NH2 2. H3O+

N

1. LiAlH4 2. H3O+

NH2

Weinreb Amides Only React with Grignards Once

How to Synthesis Amino Acids (Section 17.4) Hell-VolhardZelinsky Bromination Reductive Amination of Oxo Acids Combined Malonic Ester/Gabriel Synthesis

The Strecker Synthesis

Dipeptide Synthesis (Section 17.5) Stage 1: t-Boc protect the Nterminus

Stage 2: esterify the O-terminus

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Stage 3: peptide couple and deprotect

Monosaccharide Reactions (Section 18.4)

NaBH4 Reduction

Br2 Oxidation

HNO3 Oxidation

Glycoside Formation

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Kiliani–Fischer Synthesis

(lengthens monosaccharides)

Wohl Degradation (shortens monosaccharides)

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