Chapter 4

The
Reactions of
Alkenes/Alky
nes
The
Stereochemistry of
Addition Reactions

Alkene Reactions in Chapter 4

name

class

1.
Hydrohalogenatio
n

electrophili hydrochlorinati
c addition
on,
hydrobrominati
on,
hydroiodination
electrophili
c addition
electrophili bromination,
c addition
chlorination
electrophili reduction
c addition
oxidation

2. Hydration
3. Halogenation
4. Hydrogenation

subclass

mechani
sm
yes

yes
yes
no

5. cis Dino
hydroxylation
Refer
to the course map in
the syllabus when
studying the remainder
6.
Oxidative
oxidation

no
of the material in this course as we will not cover every reaction in the
cleavage
textbook.
Always refer tooxidation
the 345 reactions
summary in the
7.
Epoxidation

nocourse
materials folder in Blackboard. If the reaction has a yes under the
mechanism column, you are expected to learn the mechanism that
goes along with the reaction.

Alkene Substitution Patterns

Addition of Hydrogen Halides

Et2O

Et2O

Et2O = diethyl ether = solvent only

Which sp2 Carbon Gets the H+?

Et2O

The Mechanism

Carbocation formation is the rate-limiting step.

Why the Difference in Rate?

The more stable carbocation is formed more rapidly.

The Difference in Carbocation Stability

Determines the Products

Et2O

What Product Will Be Formed?

Formation of a Racemic Mixture

Carbocation Stability and Product

Distributions
All carbocations are reactive intermediates
Secondary carbocations are less stable than
tertiary carbocations but can form during the
course of a reaction
Products cannot be derived from methyl and
primary carbocations
Methyl carbocations only form under special
circumstances
If a primary carbocation forms, it will quickly
rearrange to a more stable form.

Alkene Hydration: Alcohol Synthesis

Mechanism for the Acid-Catalyzed

Hydration

Formation of an Ether
A Variation of Hydration

Halogenation: Addition of Br2 or Cl2

CCl4

CCl4
Product is a 1,2 dihalide (vicinyl dihalide)
Carbon tetrachloride (CCl4) is the reaction solvent and
does not participate in the reaction

The Mechanism for

the Addition of a Halogen

CCl4

The intermediate is a cyclic bromonium ion.

The Mechanism for

the Addition of a Halogen

Bromonium ion

Bromonium ion in 3-D

Addition of a Halogen is an Anti Addition

Formation of a Bromohydrin
A Variation on Halogenation

In this reaction, the solvent is water not CCl4. Since water

is a nucleophile it can ring open the bromonium ion.
Water is in much higher concentration than bromide anion.

Hydrogenation Addition of H2 across

a double bond

catalytic hydrogenation
a reduction reaction

Mechanism for Hydrogen Addition

catalytic hydrogenation

Hydrogenation Undergoes Syn Addition

Cis Dihydroxylation (pg 509-510)

Mechanism proceeds through a osmate
ester. You are responsible for knowing only
the functional group transformation not
the mechanism

Syn addition

Cis Dihydroxylation

Draw eclipsed

Drawn staggered

Optically active?

Oxidative Cleavage
Like hydrogenation, products depend on the substitution of the
starting alkene. Note that the intermediate aldehydes cannot be
isolated under these strongly oxidative conditions. Instead, they
are further oxidized to carboxylic acids.

(CO2)

Oxidative Cleavage
Mechanism proceeds through a manganate ester. You
are responsible for knowing only the functional group
transformation not the mechanism

Oxidative Cleavage
Products depend on the substitution of the starting
alkene sp2 to 1s bonds are fully oxidized

Expoxidation
Epoxides are strained three-member cyclic ethers
Like bromonium ions, nucleophiles may ring open
expoxides

MCPBA is a Commonly Used Peroxyacid

CH2Cl2

Precipitates out of
solution as epoxide
is formed

Mechanism for Epoxidation

You are not responsible for knowing this mechanism

the mechanism is similar to that for the addition of Br 2

Syn Addition to a cis Isomer

Forms Only the cis Stereoisomers

Syn Addition to a trans Isomer

Forms Only the trans Stereoisomers

Strained Epoxides Ring Open

Recall the formation of a bromohydrin from the ring opening of a
bromonium ion

Nucleophiles can also ring open epoxides with the same

stereochemical result

Formation of cis and trans Diols

Consider the complementary reactions below

With the chemistry you now have, both products are available to
you.

Nomenclature of Epoxides

Alkynes

Nomenclature
Structure
Reduction
Acid/base chemistry
Carbon-carbon bond
forming reactions

Nomenclature of Alkynes
An alkyne is a hydrocarbon that contains a carboncarbon triple bond.
General formula: CnH2n2 (acyclic)
CnH2n4 (cyclic)

The Structure of Alkynes

The triple bond is composed of a sigma bond and two bonds.

Alkynes Are Less Stable and

Less Reactive Than Alkenes

Addition of Hydrogen Forms an Alkane

Stopping at the Alkene

Lindlar Catalyst

Syn Addition

Why Cis?

The catalyst delivers the hydrogens to one side of the triple bond.

Relative Electronegativities of Carbon

Remember from chapter 2:
sp hybridized carbons have 50% s character and 50% p character
sp2 hybridized carbons have 33% s character and 66% p character
sp3 hybridized carbons have 25% s character and 75% p character

A Hydrogen Attached to an sp Carbon

is the Most Acidic
Remember from Chapter 2, the more s character, the closer the electrons are
to the offsetting nuclear charge and that results in the pKa values of alkynes,
alkenes, and alkanes

Amide ion the conjugate base of ammonia

Used to deprotonate acids with pKa values outside of water

pKa = 25

pKa = 35

HO is Not Strong Enough

pKa = 25

pKa = 15

Forming a New CarbonCarbon Bond

Mechanism for Formation of the

CarbonCarbon Bond

Two Steps

Designing a Synthesis
all reactions covered
in chapter 3
?
Me

Et

Me

H 2, Linlar

NaNH 2/NH3
Me

EtBr

Et

Me