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Organic Chemistry
6th Edition Chapter 4
Paula Yurkanis Bruice

The Reactions of
Alkenes

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Electrophilic Addition of Alkenes:

Reaction and Synthesis

Reaction of an alkene is
an addition reaction.

synthesis of an alkene
an elimination reaction
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Electrophilic Addition of Alkenes

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Addition of Hydrogen Halides

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What is the product?

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Carbocation Formation Is the Rate-

Limiting Step
a more stable
carbocation

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Carbocation Stabilities

Alkyl groups decrease the concentration of positive

charge in the carbocation 7
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Stabilization of a Carbocation

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Species Stability Predicted by

Hyperconjugation
Radical Stability

Carbocation Stability

Carbanion Stability

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Molecular Orbital Diagram in a

Hyperconjugation System

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Hammond postulate: the transition state will be more

similar to the species that it is closer to energetically

Exergonic reaction: early transition state

Endergonic reaction: late transition state

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The transition state is more similar in structure to the

species to which it is more similar in energy 12
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Reaction Coordinate Diagram for the

Addition of H+ to 2-Methylpropene

In an electrophilic addition reaction, the more stable

carbocation forms faster.
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Electrophilic Addition Reactions Are

Regioselective

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Markovnikov’s Rule
The electrophile adds to the sp2 carbon that is bonded to
the greater number of hydrogens:

In a regioselective reaction, one constitutional isomer is the

major or the only product.

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Addition of Water to Alkene

What is the electrophile?

What nucleophile is present in the greatest concentration?
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Acid Catalyzed Addition of Alcohol

Mechanism:

Varying the alkene and alcohol starting

materials will afford structurally diverse
ether products:

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The Fate of Carbocations:

• Carbocations can trap nucleophiles:

• Carbocations can rearrange:

• Carbocations can trap alkene nucleophiles:

• Carbocations can lose a proton to afford an alkene:

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Rearrangement of Carbocations
1,2-hydride shift a more stable
carbocation

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Rearrangement of Carbocations
a more stable
1,2-methyl shift carbocation

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A carbocation does not always

rearrange:

Why? Because rearrangement has not resulted

in a more a stable carbocation.

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Carbocation Rearrangement
with Ring Expansion

Rearrangement favored by relief of

ring strain and tertiary carbocation
formation.

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Carbocation Reactions in Nature

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Addition of a halogen to an alkene

Mechanism for the addition of bromine to an alkene

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Bromonium Ion Formation

The same reaction with chlorine

affords a chloronium ion:
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Addition of Halogens in the Presence of

Water or Alcohol
Addition of halogens to an alkene in the presence of water affords a
halohydrin, a compound with an alcohol and a halogen on adjacent
carbons.

Addition of halogens to an alkene in the presence of a primary

alcohol affords a halo ether by the same mechanism.

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Trapping of the Bromonium or Chloronium Ion

by Nucleophilic Solvents Is Regioselective
Consider the two possible transition states:

Therefore:

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Oxymercuration of an Alkene

Trapping of the cyclic mercurium

ion by water is regioselective:

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Demercuration by Reduction
Reduction increases the number of C-H bonds or
decreases the number of C-O, C-N, or C-X bonds

Reduction Mechanism:

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The Oxymercuration-Demercuration Reaction

• A means of avoiding rearrangements

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Addition of a Peroxyacid to an Alkene

An Oxidation Reaction

Oxidation decreases the number of C-H bonds or

increases the number of C-O, C-N, or C-X bonds

Mechanism of epoxidation:

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Naming of Epoxide
There are three ways of naming an epoxide:
• As an epoxy-substituted alkane.
• As an alkene, just add the word oxide for an epoxy
compound.
• As an oxirane ring derivative.
Alkene Oxide Naming

Alkane and Oxirane Naming

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The Hydroboration Reaction

Formally the Anti-Markovnikov addition of water

Anti-Markovnikov
addition of water

Markovnikov
addition of water

Hydroboration is a two-step process:

1. Trialkylborane formation
2. Hydroperoxide and base treatment

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Alkylborane Formation
A pericyclic reaction:

Regioselectivity due to carbocation formation is the transition state

and steric interaction between borane and the alkene substituents :

Anti-Markovnikov Addition Markovnikov Addition

of BH3 favored. of HBr favored 34
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Trialkylborane Formation
Insertion of B-H bonds into alkene bonds continues
until the trialkylborane is formed:

Driving force for trialkylborane formation:

Stabilization of the vacant boron p-orbital by
hyperconjugation.
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Oxidation of theTrialkylborane Followed

by Base-Catalyzed Hydrolysis Borate Ester,
the Oxidation
Product
Treatment with hydrogen peroxide in aqueous hydroxide:

Hydrolysis:Bond Cleavage
Mediated by a Water
Component, i.e. Hydroxide

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Hydroboration Examples

Do not forget to number the reagents.

This is a two-step reaction!
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Addition of Hydrogen to Alkenes

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Catalytic Hydrogenation of an Alkene

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Potential Energies of Pentene Isomers

The most stable alkene has the

smallest heat of hydrogenation.
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Relative Stabilities of
Alkyl-Substituted Alkenes

•Alkyl substituents stabilize both alkenes and

carbocations.
•The most stable alkene has the greatest number of alkyl
groups bonded to its sp2 carbon.
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Steric Strain in Alkenes

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Partial Hydrogenation
Cis - Alkene Cis - Alkene

Unsaturated fat with cis double bonds.

An oil at room temperature.
Saturated Chain Partially
Saturated Chain

Partially saturated fat with cis and the

Trans - Alkene
relatively stable trans double bond.
A butter-like solid at room temperature.
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