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
