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Organic Chemistry Reaction Summary Sheet, Cheat Sheet of Organic Chemistry

Alkene, Alkyne, Diels Alder, Grignard, EAS, Diazonium Salt, Hydride Reduction and many more reactions are here

Typology: Cheat Sheet

2020/2021

Uploaded on 04/26/2021

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Organic Chemistry Reaction Summary Sheet
Alkene Reactions
Hydrohalogenation
Hydrohalogenation
(with Rearrangement)
Halogenation
Hydrobromination
with Peroxide
Hydration
Hydration (with
Rearrangement)
Bromination in H2O
Oxymercuration-
Demurcuration
Hydroboration-
Oxidation
Syn-Dihydroxylation
Syn-Dihydroxylation
Anti-Dihydroxylation
Addition of an Alcohol
Bromination in Alcohol
Alkoxymercuration-
Demurcuration
Epoxidation
pf3
pf4
pf5
pf8
pf9
pfa
pfd
pfe
pff
pf12
pf13
pf14
pf15
pf16
pf17
pf18
pf19
pf1a
pf1b
pf1c
pf1d
pf1e

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Organic Chemistry Reaction Summary Sheet

Alkene Reactions

Hydrohalogenation

Hydrohalogenation (with Rearrangement)

Halogenation

Hydrobromination with Peroxide

Hydration

Hydration (with Rearrangement) Bromination in H 2 O

Oxymercuration- Demurcuration

Hydroboration- Oxidation

Syn-Dihydroxylation

Syn-Dihydroxylation

Anti-Dihydroxylation

Addition of an Alcohol

Bromination in Alcohol

Alkoxymercuration- Demurcuration

Epoxidation

Catalytic Hydrogenation Pt can also be used Ozonolysis (Reducing Conditions)

Ozonolysis (Oxidizing Conditions)/Oxidative Cleavage

Alkyne Reactions

Catalytic Hydrogenation (Catalytic Reduction) Reduction to Cis- Alkene Reduction to Trans- Alkene Hydrohalogenation with HBr (Terminal Alkyne) Hydrohalogenation with HBr (Internal Alkyne) Halogenation with Br 2

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 SN 2 Addition of an Acetylide Ion to an Epoxide

  1. O 3
  2. H 2 O 2 or
  3. KMnO 4 /heat
  4. H 3 O+

O

O

OH

H 2

Lindlar’s Catalyst

Diene Addition to a trans Dienophile

Diene Addition to a substituted Dienophile

Grignard Reactions

Addition of a Grignard Reagent to an Aldehyde 2˚Alcohol

Addition of a Grignard Reagent to a Ketone 3˚Alcohol

Addition of a Grignard Reagent to an Ester 3˚Alcohol

Addition of a Grignard Reagent to an Acyl Chloride

3˚Alcohol Addition of a Grignard Reagent to CO 2

Carboxylic Acid

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

Addition of a Grignard Reagent to a Carboxylic Acid

Carboxylate

hv or

enantiomers

hv or

O

O

O

endo (Major)

exo (Minor)

H

H

H

H

H

H

O

H

H

O

  1. MgX, Ether
    1. H 3 O+

O OH

MgX OH

O

  1. , Ether
    1. H 3 O+^ O

O

MgX

  1. CO 2 , Ether
    1. H 3 O+

MgX

O

OH

  1. (^) MgX, Ether
    1. H 3 O+

O HO

MgX O

O (^) 1. 2 eq. , Ether

  1. H 3 O+

HO

MgX Cl

O (^) 1. 2 eq. , Ether

  1. H 3 O+

HO

  1. (^) MgX, Ether H 2. H 3 O+

O OH

Addition of a Grignard Reagent to an Amide

Deprotonated Amide

Addition of a Grignard Reagent to a Nitrile Ketone

Electrophilic Aromatic Substitution (EAS) Reactions

Friedel-Crafts Alkylation (Rearrangement Possible)

Friedel-Crafts Acylation (No Rearrangement Possible)

Bromination

Chlorination

Nitration

Sulfonation

Formylation

MgX NH (^2)

O

  1. , Ether
    1. H 3 O+^ NH

O

MgX

Cl AlCl (^3)

Cl AlCl (^3)

FeCl (^3)

Cl Cl 2

H 2 SO 4

SO 3 H

SO 3

H 2 SO 4 /Δ

MgX

  1. , Ether O
    1. H 3 O+

N

Cl AlCl (^3)

O O

H 2 SO 4

HNO NO^2

3

AlCl (^3)

CO, HCl

O

H

FeBr 3

Br2 Br

Acetylation of Aniline using Acetic Anhydride

Diazonium Salt Reactions

Hydride Reduction Reactions

Reduction of an Aldehyde to a 1˚Alcohol

Reduction of a Ketone to a 2˚Alcohol

Reduction of a Carboxylic Acid to a 1˚Alcohol

Reduction of an Ester to a 1˚Alcohol

NH 2

H

N

O O

O O

pyridine Aniline Acetanilide

NaNO 2 , HCl (HONO)

NH 2 N 2 +

CuBr or CuCl Br or Cl

CN

CuCN

I

KI

H

3 O

or EtOH

OH

F

HBF

4

H 3 PO 2

H

O (^) 1. NaBH (^4)

  1. H 3 O+^ H

OH

H

O (^) 1. LiAlH (^4)

  1. H 3 O+^ H

OH

O (^) 1. NaBH (^4)

  1. H 3 O+

OH

O (^) 1. LiAlH (^4)

  1. H 3 O+

OH

OH

O (^) 1. LiAlH (^4)

  1. H 3 O+^ H

OH

O

O (^) 1. LiAlH (^4)

  1. H 3 O+^ H

OH

OH

Reduction of an Ester to an Aldehyde

Reduction of an Acyl Chloride to a 1˚Alcohol

Reduction of an Acyl Chloride to an Aldehyde

Reduction of an Amide to an Amine

Hoffmann Rearrangement

Reduction of a Nitrile to an Amine

Alcohol Reactions

Conversion of a 2˚/3˚Alcohol to an alkyl halide via SN 1

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

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

Conversion of an Alcohol to a Tosylate Ester (OTs) Retention of Stereochemistry

Acid-catalyzed Dehydration of an Alcohol Zaitsev’s Rule

Cl

O (^) 1. LiAlH (^4)

  1. H 3 O+^ H

OH

NH 2

O (^) 1. LiAlH (^4)

  1. H 3 O+^ NH^2
  2. LiAlH (^4)
  3. H 3 O+^

N NH 2

OH (^) PBr 3 Br

O LiAlH[OC(CH 3 ) 3 ] 3 Cl

O

H

OH HX X

OH HX X

OH (^) SOCl 2 Cl Pyridine

H

OH (^) PBr 3 H

Br

H

OH (^) SOCl 2 H

Cl Pyridine

OH

H 3 O+

OH (^) TsCl OTs

O

O 1. DIBAL-H, -78°C

2. H 2 O H

O

NH 2

O (^) 1. Br 2

  1. NaOH

NH 2

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

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

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

Aldehyde and Ketone Reactions

Nucleophilic Addition to an Aldehyde or Ketone

Addition of water to an Aldehyde or Ketone forming a Hydrate

Base-catalyzed addition of an Alcohol to an Aldehyde or Ketone forming a Hemi-acetal/Hemi-ketal Acid-catalyzed addition of an Alcohol to an Aldehyde or Ketone forming a Acetal/Ketal (Protecting Group, reversed by H 3 O+)

Acid-catalyzed addition of Ethylene Glycol to an Aldehyde or Ketone forming a Acetal/Ketal (Protecting Group, reversed by H 3 O+)

Addition of a 1˚ Amine to an Aldehyde or Ketone forming an Imine (Reversed by H 3 O+)

O HCl OH

Cl

O (^) HBr OH Br

C or H

O

C or H

O HO^ O

HO

C or H

O

C or H

Nucleophile HO H 3 O+

Nucleophile

C or H

O

H 3 O+^ or - OH

H 2 O

C or H

HO OH

C or H

O

C or H

O O

H 3 O+

H 3 O+

HO

OH

C or H

O

C or H

O O

HO

H 3 O+

H 3 O+

O OCH 3

HOCH 3

O

OH

C or H

O

C or H

N

H 3 O+

H 2 N

H 3 O+

O H 3 O+

OH

OH

Addition of a 2˚ Amine to an Aldehyde or Ketone forming an Enamine (Reversed by H 3 O+)

Double bond forms on more substituted end for Ketones Addition of a Wittig Reagent to an Aldehyde or Ketone

Michael Addition to an α, β Unsaturated Ketone

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

Nitrile Reactions

Acid-catalyzed Hydrolysis of a Nitrile

SN2 formation of Nitriles using Cyanide and Alkyl Halides

Cyanohydrin Formation using Aldehydes/Ketones and Cyanide

OH

H O

C N^3 O+, Heat

X C

N

C N

C or H C or H

C N

O HO CN

C or H

O

H 3 O+

N

H

H 3 O+

C or H

N

C or H

O

C or H

PPh (^3)

O O

O O

or -^ CN, HNR 2 , HSR etc.

O

O

O O

(CH 3 CH 2 CH 2 ) 2 CuLi

Dieckmann Cyclization (Intramolecular Claisen Condensation) Acetoacetic Ester Synthesis

Malonic Ester Synthesis

Alpha Halogenation In Basic Conditions

Alpha Halogenation in Acidic Conditions

Haloform Reaction

*A methyl group is required for this reaction

O

  1. NaOH
  2. X 2 (excess)

O

X X

X X

X X

O (^) 1. Acid (TFA)

  1. X 2

O

X

O

O O

1. O

  1. Cl
  2. O
  3. Cl
  4. H 3 O+, Δ

O

CO 2 HO

O O

O O

1. O

  1. Cl
  2. O
  3. Cl
  4. H 3 O+, Δ

HO

O

CO 2 2 HO

1. O

2. H 3 O+^

O

O

O O

O O O

R or H

O

X 2 (excess) NaOH (^) R or H O

O

CHX 3

DAT Organic Chemistry Reaction Details Sheet

Rearrangements Details

When carbocations form, H’s and CH 3 ’s can do a 1,2-shift to generate a more stable carbocation intermediate

1,2-Hydride Shift

1,2-Methyl Shift

Alkene Reaction Details

Hydrohalogenation

What’s added: H+ and Br- Regioselectivity: Markovnikov Stereoselectivity: N/A Intermediate: Carbocation Rearrangement: Possible (methyl and hydride shifts) Mechanism:

Hydration

What’s added: H+^ and OH- Regioselectivity: Markovnikov Stereoselectivity : N/A Intermediate: Carbocation Rearrangement: Possible (methyl and hydride shifts) Mechanism:

Bromination in H 2 O

What’s added: Br+^ and OH- Regioselectivity: Markovnikov Stereoselectivity : Anti Intermediate: Bromonium ion Rearrangement: Not possible Mechanism:

Oxymercuration-Demercuration

What’s added: H+^ and OH- Regioselectivity: Markovnikov Stereoselectivity : Anti Intermediate: Mercurinium ion bridge Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction

Hydroboration-Oxidation

What’s added: H+^ and OH- Regioselectivity: Anti-Markovnikov Stereoselectivity : Syn Intermediate: Hydroxy-boranes Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction

Syn-Dihydroxylation

or

What’s added: 2 OH groups Regioselectivity: N/A Stereoselectivity : Syn Intermediate: N/A Rearrangement: Not possible Mechanism:

Anti-Dihydroxylation

What’s added: 2 OH groups Regioselectivity: N/A Stereoselectivity : Anti Intermediate: N/A Rearrangement: Not possible Mechanism: Epoxidation then reaction with aqueous acid or base. In acidic conditions, the H 2 O attacks the more highly-substituted C:

In basic conditions, H 2 O attacks the less highly-substituted C:

Epoxidation

What’s added: O Regioselectivity: N/A Stereoselectivity : Syn Intermediate: N/A Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction Do know that a commonly-used peroxy acid is m -CPBA:

Catalytic Hydrogenation

What’s added: 2 H atoms Regioselectivity: N/A Stereoselectivity : Syn Intermediate: N/A Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction Note: You may see Pt used as well. This is just the catalyst and does not change the outcome of the products.

Ozonolysis in Reducing Conditions

What’s added: 2 O atoms Regioselectivity: N/A Stereoselectivity : N/A Intermediate: N/A Rearrangement: N/A Mechanism: You do not need to know the mechanism for this reaction

Do know that the C=C double bond gets “sawed” in half, and an O atom is placed on the end of each new piece. Note: (CH 3 ) 2 S is often abbreviated “DMS” for dimethyl sulfide.

Ozonolysis in Oxidizing Conditions/Oxidative Cleavage

What’s added: Multiple O atoms Regioselectivity: N/A Stereoselectivity : N/A Intermediate: N/A Rearrangement: N/A Mechanism: You do not need to know the mechanism for this reaction

Know that the C=C double bond gets “sawed” in half, and an O atom is placed on the end of each new piece. Any H’s attached to the alkene C’s get replaced by an –OH group since we are under oxidizing conditions/hot KMnO 4. Unlike reducing conditions which would have formed aldehydes, oxidizing conditions produces carboxylic acids instead.

Alkyne Reaction Details

Catalytic Hydrogenation

What’s added: 4 H atoms Regioselectivity: N/A Stereoselectivity : Anti Intermediate: N/A Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction. Note: You may see Pt used as well. This is just the catalyst and does not change the outcome of the products.

Reduction to Cis-Alkene

  1. O 3
  2. H 2 O 2 or
  3. KMnO 4 /heat
  4. H 3 O+

O

O

OH

  1. O 3
  2. H 2 O 2 or
  3. KMnO 4 /heat
  4. H 3 O+

O

O

OH

H 2

Lindlar’s Catalyst

What’s added: 2 H atoms Regioselectivity: N/A Stereoselectivity : Syn Intermediate: N/A Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction