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

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

Ozonolysis (Oxidizing 1. O3
2. H2O2 O
Conditions)/Oxidative
Cleavage or O OH
1. KMnO4/heat
2. H3O+

Alkyne Reactions

Catalytic
Hydrogenation
(Catalytic Reduction)
Reduction to Cis- H2
Alkene Lindlar’s Catalyst
Reduction to Trans-
Alkene
Hydrohalogenation
with HBr (Terminal
Alkyne)
Hydrohalogenation
with HBr (Internal
Alkyne)
Halogenation with Br2

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
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EAS with an ortho/para- O/P O/P O/P
directing group on Substituent
Substituent
Benzene

Substituent
EAS with a meta-directing M M
group on Benzene
Substituent

Substituent
Friedel-Crafts M O
Alkylation/Acylation with a
R Cl or Cl R
meta-directing group or No Reaction
an amine on Benzene AlCl3

NH2/NRH/NR2 O
R Cl or Cl R No Reaction
AlCl3

Benzene Side-Chain Reactions

Side-Chain Oxidation of R O
1. KMnO4, -OH
Benzene to form Benzoic
R R 2. H3O+, Heat OH
Acid
or or or
Na2Cr2O7
H2SO4
1. KMnO4, -OH

2. H3O+, Heat
No Reaction (Requires free Hydrogen
or
at Benzylic position)
Na2Cr2O7
H2SO4

Wolff-Kishner Reduction O
H2NNH2 or N2H4, -OH, Heat

Clemmensen Reduction O
Zn(Hg), HCl, Heat

*can also use H2/Pd, C

NO2 Zn(Hg), HCl, Heat NH2

*can also use H2/Pd, C or Sn/HCl

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Acetylation of Aniline using H
NH2 O O N
Acetic Anhydride
O O
pyridine
Aniline Acetanilide

Diazonium Salt Reactions

NH2 N 2+
NaNO2, HCl H3PO2
(HONO)
l
CuC HB
or F
r 4
B
Cu

H 3O
F
CN

+
Br or Cl

or
Cu

KI

EtO
CN
I H
OH

Hydride Reduction Reactions

Reduction of an Aldehyde to O 1. NaBH4 OH

a 1˚Alcohol
H 2. H3O+ H

O 1. LiAlH4 OH

H 2. H3O+ H
Reduction of a Ketone to a O 1. NaBH4 OH
2˚Alcohol
2. H3O+

O 1. LiAlH4 OH

2. H3O+
Reduction of a Carboxylic O 1. LiAlH4 OH
Acid to a 1˚Alcohol
OH 2. H3O+ H

Reduction of an Ester to a O 1. LiAlH4 OH

1˚Alcohol OH
O 2. H3O+ H

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

H3O+

Double bond forms on more substituted end for Ketones

Addition of a Wittig Reagent to an
O PPh3
Aldehyde or Ketone
C or H C or H
Michael Addition to an α, β Unsaturated O O
Ketone O O

or -CN, HNR2,
HSR etc.
O

O
Michael Addition to an α, β Unsaturated
O O
Ketone with a Gilman Reagent (CH3CH2CH2)2CuLi
(Organocuprates)

Nitrile Reactions

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
N
Cyanohydrin Formation using N
O HO C
Aldehydes/Ketones and Cyanide C N
C or H C or H

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Carboxylic Acid Derivative Reactions
SOCl2
O

R Cl

Acyl Chloride

O O
O
R O R’
R‘ OH or
Acid Anhydride O
O
R OH
R‘ O O H3O+/Heat
Carboxylic Acid
R’OH or R’O- R OR’ R’OH/H+

at
Ester

/He
3O +
H
H+ H3O+
H+
O

R NR’2
R2NH
or Amide
R2N -
O

R O
-OH
Carboxylate

Alpha Addition/Substitution Reactions

Self Aldol O O OH
-OH, H 2O H3O+, NaOH O
Condensation
2 H H Δ
and Enone H
Formation
O O O
-OH, H 2O OH H3O+, NaOH
2 Δ
Mixed Aldol O O O OH
-OH, H3O+, NaOH O
Condensation H 2O
H Δ
and Enone
Formation

O O
O O -OH, H 2O H3O+, NaOH
Δ
HO
Self Claisen
Condensation O O O
1. O
2 O O
2. H3O+

Mixed Claisen
Condensation O O O O
1. O
O 2. H3O+

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Hydration

What’s added: H+ and OH-

Regioselectivity: Markovnikov
Stereoselectivity: N/A
Intermediate: Carbocation
Rearrangement: Possible (methyl and hydride shifts)
Mechanism:

Bromination in H2O

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

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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 H2O attacks the more highly-substituted C:

In basic conditions, H2O attacks the less highly-substituted C:

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Reduction to Trans-Alkene

What’s added: 2 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

Hydrohalogenation with HBr (Terminal Alkyne)

What’s added: 1 H atom and 1 halogen atom (can be F, Br, I, or Cl) per equivalent of HX
Regioselectivity: Markovnikov
Stereoselectivity: N/A
Intermediate: Carbocation
Rearrangement: Not possible
Mechanism: The halogen goes to the C with fewer H’s

Hydrohalogenation with HBr (Internal Alkyne)

What’s added: 1 H atom and 1 halogen atom (can be Cl or Br) per equivalent of HX
Regioselectivity: Markovnikov
Stereoselectivity: N/A
Intermediate: Carbocation
Rearrangement: Not possible
Mechanism: Same as for terminal alkynes, but yields a mixture of two products because both intermediates are equally
stable

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Halogenation with Br2

What’s added: 2 halogen atoms (can be F, Br, I, or Cl)

Regioselectivity: N/A
Stereoselectivity: Anti
Intermediate: Bromonium ion
Rearrangement: Not possible
Mechanism:

Hydration of an Internal Alkyne

What’s added: 1 O atoms

Regioselectivity: N/A
Stereoselectivity: N/A
Intermediate: N/A
Rearrangement: Not possible
Mechanism: You do not need to know the mechanism for this reaction
Do know that this reaction produces enols, which then tautomerize to form ketones.

Hydration of a Terminal Alkyne (Markovnikov)

What’s added: 1 O atom

Regioselectivity: Markovnikov
Stereoselectivity: N/A
Intermediate: N/A
Rearrangement: Not possible
Mechanism: You do not need to know the mechanism for this reaction

Do know that this reaction produces Markovnikov enols, which then tautomerize to form ketones.
OH tautomerism O

enol (Markovnikov) ketone

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Free Radical Halogenation Reaction Details

Free Radical Halogenation using Bromine (more selective)

Br
Br2
hv or Δ

What’s added: 1 Br atom

Regioselectivity: Most Substituted Product
Stereoselectivity: N/A
Intermediate: Radical Intermediate
Rearrangement: Not possible
Mechanism: Formation of bromine and carbon radicals and them joining to create an alkyl halide

1. Initiation

hv or Δ
Br Br Br Br

2. Propagation

H
Br
HBr

Br
Br Br Br

alkyl halide

3. Termination

Br Br Br Br

Free Radical Halogenation using Chlorine (less selective)

Cl

Cl2 Cl

hv or Δ Cl

Cl
What’s added: 1 Cl atom
Regioselectivity: N/A
Stereoselectivity: N/A
Intermediate: Radical Intermediate
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Rearrangement: Not possible
Mechanism: Formation of chlorine and carbon radicals and them joining to create alkyl halides

1. Initiation

hv or Δ
Cl Cl Cl Cl

2. Propagation

H
H
Cl Cl
HCl HCl
Cl

Cl
Cl Cl Cl Cl Cl Cl
alkyl halide
alkyl halide

Cl H Cl
HCl HCl

Cl Cl
Cl Cl
Cl Cl
alkyl halide Cl

Cl
alkyl halide

3. Termination

Cl Cl Cl Cl

Allylic/Benzylic Bromination

NBS Br
hv or Δ
or ROOR

NBS Br
hv or Δ
or ROOR Br

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