John E.
McMurry
www.cengage.com/chemistry/mcmurry
Chapter 8
Alkenes: Reactions and
Synthesis
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Learning Objectives
(8.1)
Preparing alkenes: A preview of elimination reactions
(8.2)
Halogenation of alkenes: Addition of X 2
(8.3)
Halohydrins from alkenes: Addition of HOX
(8.4)
Hydration of alkenes: Addition of H2O by oxymercuration
(8.5)
Hydration of alkenes: Addition of H2O by hydroboration
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Learning Objectives
(8.6)
Reduction of alkenes: Hydrogenation
(8.7)
Oxidation of alkenes: Epoxidation and hydroxylation
(8.8)
Oxidation of alkenes: Cleavage to carbonyl compounds
(8.9)
Addition of carbenes to alkenes: Cyclopropane
synthesis
(8.10)
Radical additions to alkenes: Chain-growth polymers
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Learning Objectives
(8.11)
Biological additions of radicals to alkenes
(8.12)
Reaction stereochemistry: Addition of H 2O to an achiral
alkene
(8.13)
Reaction stereochemistry: Addition of H 2O to a chiral
alkene
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Diverse Reactions of Alkenes
Alkenes react with many electrophiles to give
useful products by addition
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Preparation of Alkenes: A Preview
of Elimination Reactions
Alkenes are commonly made by elimination
reaction
Dehydrohalogenation - Loss of HX from an alkyl
halide
Occurs by reaction of an alkyl halide with strong
base
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Preparation of Alkenes: A Preview
of Elimination Reactions
Dehydration - Loss of water from an alcohol
Carried out by treating an alcohol with a strong acid
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Worked Example
How many alkene products, including E,Z
isomers, might be obtained by dehydration of 3methyl-3-hexanol with aqueous sulfuric acid?
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Worked Example
Solution:
It is possible to obtain five alkene products by the
dehydration of 3-methyl-3-hexanol
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Halogenation of Alkenes:
Addition of X2
Halogenation - Bromine and chlorine add to
alkenes to give 1,2-dihalides
Example
1,2-dichloroethane is formed by addition of Cl2 to
ethylene
Fluorine is too reactive and iodine does not react
with majority of alkenes
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Halogenation of Alkenes:
Addition of X2
Halogenation reaction of cycloalkane forms the
trans stereoisomer of the dihalide addition
product
Reaction occurs with anti stereochemistry
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Mechanism of Bromine Addition
As suggested by George Kimball and Irving
Roberts, for the observed stereochemistry the
reaction intermediate is not a carbocation
Bromonium ion, R2Br+, is formed by
electrophilic addition of Br+ to the alkene
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Mechanism of Bromine Addition
Bromonium ion is formed in a single step
Interaction of the alkene with Br2 and
simultaneous loss of Br Reaction with Br- ion occurs only from the
opposite, unshielded side to give trans product
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Mechanism of Bromine Addition
Bromonium ions were postulated more than 75
years ago to explain stereochemistry of halogen
addition to alkenes
George Olah showed that bromonium ions are
stable in liquid SO2
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Worked Example
Addition of HCl to 1,2-dimethylcyclohexene
yields a mixture of two products
Show the stereochemistry of each, and explain
why a mixture is formed
Solution:
Addition of hydrogen halides involves formation of an
open
carbocation
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Worked Example
The carbocation, which is sp2-hybridized and
planar, can be attacked by chloride from either
top or bottom
This yields products in which the two methyl
groups can be either cis or trans to each other
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Halohydrins from Alkenes:
Addition of HOX
Reaction of alkenes with hypohalous acids HO
Cl or HOBr yields 1,2-halo alcohol, called a
halohydrin
Addition takes place by reaction of the alkene
with either Br2 or Cl2 in the presence of water
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Figure 8.1 - Mechanism
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Halohydrins from Alkenes:
Addition of HOX
Bromohydrin formation is carried out in a solvent
such as aqueous dimethyl sulfoxide, CH3SOCH3
(DMSO), using the reagent N-bromosuccinimide
(NBS)
Produces bromine in organic solvents and is a
safer source
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Worked Example
What product would you expect from the
reaction of cyclopentene with NBS and water?
Show the stereochemistry
Solution:
Br and OH are trans in the product
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Hydration of Alkenes: Addition
of H2O by Oxymercuration
Hydration of an alkene is the addition of H 2O to
give an alcohol
Reaction takes place on treatment of the alkene
with water and a strong acid catalyst
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Figure 8.2 - Mechanism
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Hydration of Alkenes: Addition
of H2O by Oxymercuration
Acid-catalyzed hydration of isolated double
bonds is uncommon in biological pathways
Fumarate is hydrated to give malate as one step
in the citric acid cycle of food metabolism
In the laboratory, alkenes are often hydrated by
the oxymercurationdemercuration procedure
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Oxymercuration Intermediates
Reaction is initiated by electrophilic addition of
Hg2+ ion to the alkene
Gives an intermediate mercurinium ion
Regiochemistry of the reaction corresponds to
Markovnikov addition of H2O
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Worked Examples
What products would you expect from
oxymercurationdemercuration of the following
alkenes?
a)
b)
Solution:
Oxymercuration is equivalent to Markovnikov
addition of H2O to an alkene
a)
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Worked Examples
b)
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Hydration of Alkenes: Addition
of H2O by Hydroboration
Hydroboration: Process involving addition of a
BH bond of borane, BH3, to an alkene to yield
an organoborane intermediate, RBH2
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Hydration of Alkenes: Addition
of H2O by Hydroboration
Alkene reacts with BH3 in THF solution, rapid
addition to the double bond occurs three times
and a trialkylborane is formed
Net effect of the two-step hydroboration
oxidation sequence is hydration of the alkene
double bond
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Hydration of Alkenes: Addition
of H2O by Hydroboration
Regiochemistry that results when an
unsymmetrical alkene is hydroborated makes
the hydroboration reaction very useful
During hydroborationoxidation of
1-methylcyclopentene, boron and hydrogen
add to the alkene from the same face of the
double bond with syn stereochemistry
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Hydroboration
Differs from other alkene addition reactions
Occurs in a single step without a carbocation
intermediate
Attachment of boron is favored
Non-Markovnikov regiochemistry occurs
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Worked Example
What alkene might be used to prepare the
following alcohol by hydroborationoxidation?
Solution:
The products result from hydroboration/oxidation
of a double bond
The OH group is bonded to the less substituted
carbon of the double bond in the starting material
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Reduction of Alkenes:
Hydrogenation
Hydrogenated: Addition of hydrogen to a
double or triple bond to yield a saturated product
Reduction: Reaction that results in gain of
electron density for carbon caused either by:
Formation between carbon and a less
electronegative atom
Bond-breaking between carbon and a more
electronegative atom
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Reduction of Alkenes:
Hydrogenation
Usually occurs with syn stereochemistry
H2 is adsorbed onto the catalyst surface
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Figure 8.5 - Mechanism
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Reduction of Alkenes:
Hydrogenation
Catalytic hydrogenation is extremely sensitive to
the steric environment around the double bond
In -pinene reduction occurs exclusively from
the bottom face
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Reduction of Alkenes:
Hydrogenation
Catalytic hydrogenation is important in the food
industry
Incomplete hydrogenation results in partial cis
trans isomerization of a remaining double bond
In biological hydrations, biological reductions
occur in two steps:
Reducing agent, NADPH, adds a hydride ion to
the double bond to give an anion
Anion is protonated by acid HA, leading to overall
addition of H2
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Figure 8.7 - Reduction of the CarbonCarbon
Double Bond in Trans-crotonyl ACP
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Worked Example
What products are obtained from catalytic
hydrogenation of the following alkenes?
a)
b)
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Worked Example
Solution:
a)
b)
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Oxidation of Alkenes:
Epoxidation and Hydroxylation
Oxidation: Reaction that results in a loss of
electron density for carbon by:
Bond formation between carbon and a more
electronegative atom
Bond-breaking between carbon and a less
electronegative atom
Alkenes oxidize to give epoxides on treatment
with a peroxyacid, RCO3H
Epoxide: Cyclic ether with an oxygen atom in a
three-membered ring
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Oxidation of Alkenes:
Epoxidation and Hydroxylation
Peroxyacids transfer an oxygen atom to the
alkene with syn stereochemistry
Treating a base with halohydrin leads to
elimination of HX and production of an epoxide
Epoxides undergo an acid-catalyzed ringopening reaction with water
Gives corresponding 1,2-dialcohol, or diol, also
called a glycol
Net result of the two-step alkene
epoxidation/hydrolysis is hydroxylation
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Oxidation of Alkenes:
Epoxidation and Hydroxylation
Hydroxylation can be carried out directly by
treating an alkene with osmium tetroxide
Reaction occurs with syn stereochemistry
Does not involve a carbocation intermediate
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Worked Example
What product is expected from reaction of cis-2-
butene with metachloroperoxybenzoic acid?
Show the stereochemistry
Solution:
Epoxidation using m-chloroperoxybenzoic acid is
a syn addition
Original bond stereochemistry is retained
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Oxidation of Alkenes: Cleavage
to Carbonyl Compounds
Ozone (O3) adds to CC bond, at low
temperature, to form molozonide
Molozonide rearranges to form ozonide
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Oxidation of Alkenes: Cleavage
to Carbonyl Compounds
Ozonide is treated with a reducing agent to
produce carbonyl compounds
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Oxidation of Alkenes: Cleavage
to Carbonyl Compounds
Oxidizing reagents other than ozone cause
double-bond cleavage
Potassium permanganate (KMnO4) can produce
carboxylic acids and carbon dioxide if hydrogens
are present on CC
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Oxidation of Alkenes: Cleavage
to Carbonyl Compounds
Alkenes can be cleaved by hydroxylation to a
1,2-diol followed by reaction of a 1,2-diol with
the periodic acid, HIO4
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Worked Example
What products would be expected from reaction
of 1-methylcyclohexene with aqueous acidic
KMnO4?
Solution:
Aqueous KMnO4 produces:
A carboxylic acid from a CC
A ketone from a double bond carbon that is
disubstituted
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Addition of Carbenes to Alkenes:
Cyclopropane Synthesis
Carbene, R2C: Neutral molecule containing a
divalent carbon with only six electrons in its
valence shell
Alkene addition is the reaction with a carbine to
yield a cyclopropane
Added symmetrically across double bonds to
form cyclopropanes
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Figure 8.8 - Mechanism
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Figure 8.9 - The Structure of
Dichlorocarbene
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Addition of Carbenes to Alkenes:
Cyclopropane Synthesis
Addition of dichlorocarbene with cis-2-pentene is
stereospecific
Stereospecific: Only a single stereoisomer is
formed as product
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Simmons-Smith Reaction
Method for preparing nonhalogenated
cyclopropanes
Does not involve a free carbene
Utilizes a carbenoid
Reaction of diiodomethane with zinc-copper
alloy produces zinc iodide
Yields corresponding cyclopropane in the
presence of an alkene
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Worked Example
What product is expected from the following reaction
Solution:
Reaction of a double bond with CH2I2 yields a
product with a cyclopropane ring that has a CH 2
group
Two different isomers can be formed, depending
on stereochemistry of the double bond
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Radical Additions to Alkenes:
Chain-Growth Polymers
Polymer: Large molecule consisting of repeating
units of simpler molecules, called monomers
Formed by polymerization
Alkenes react with radical catalysts to undergo
radical polymerization
Simple alkene polymers are called chaingrowth
polymers
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Radical Additions to Alkenes:
Chain-Growth Polymers
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Radical Additions to Alkenes:
Chain-Growth Polymers
Initiation
Few radicals are generated on heating a small
amount of benzoyl peroxide catalyst
Benzoyloxy radical loses CO2 and gives a phenyl
radical
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Radical Additions to Alkenes:
Chain-Growth Polymers
Propagation
Radical from initiation adds to alkene to generate
alkene derived radical
Process repeats to form the polymer chain
Termination
Chain propagation ends when two radical chains
combine
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Radical Additions to Alkenes:
Chain-Growth Polymers
Other alkenes give other common polymers
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Table 8.1 - Some Alkene
Polymers and Their Uses
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Worked Example
Show the monomer units required to prepare the
following polymer:
Solution:
The smallest repeating unit in each polymer is
identified and double bond is added
Monomer
H2CCHOCH3
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Biological Additions of Radicals
to Alkenes
Radical addition reactions have severe
limitations in a laboratory environment
More controlled and more common than
laboratory or industrial radical reactions
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Figure 8.10 - Pathway of Biosynthesis of
Prostaglandins from Arachidonic Acid
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Reaction Stereochemistry: Addition of
H2O to an Achiral Alkene
Majority of biochemical reactions yield products
with chirality centers
1-Butene yields an intermediate secondary
carbocation by protonation
It reacts with H2O from either the top or the
bottom
The two transition states are mirror images
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Figure 8.11 - Reaction of H2O with the
Carbocation Resulting from Protonation of 1Butene
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Reaction Stereochemistry: Addition of
H2O to an Achiral Alkene
Formation of a new chirality center by achiral reactants
leads to a racemic mixture of enantiomeric products
Optically active product can only result by starting with
an optically active reactant or chiral environment
Cis-aconitate is achiral
Only the enantiomer of the product is formed
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Reaction Stereochemistry: Addition of
H2O to a Chiral Alkene
The stereochemistry in acid-catalyzed addition
of H2O is established by reaction of H2O with a
carbocation intermediate
Does not contain a plane of symmetry
Chiral because of the chirality center at C4
Formation of a new chirality center by a chiral
reactant leads to unequal amounts of
diastereomeric products
Products are also optically active, if the chiral
reactant is optically active because only one
enantiomer is used
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Figure 8.12 - Stereochemistry of the AcidCatalyzed Addition of H2O to the Chiral Alkene
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Worked Example
What products are formed from hydration of 4-
methylcyclopentene?
Solution:
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Summary
Bromine and chlorine add to alkenes via three-
membered-ring bromonium ion or chloronium
ion intermediates to give addition products
having anti stereochemistry
If water is present during the halogen addition
reaction, a halohydrin is formed
Oxymercurationdemercuration involves
electrophilic addition of Hg2+ to an alkene
followed by subsequent treatment of the cation
intermediate with NaBH4
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Summary
Hydroboration involves addition of borane
followed by oxidation of the intermediate
organoborane with alkaline H2O2
Hydroborationoxidation gives the product with
non-Markovnikov syn stereochemistry
Catalytic hydrogenation is a process in which
alkenes are reduced by addition of H2 in the
presence of a catalyst
Alkenes are oxidized by reaction with a
peroxyacid to give epoxides
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Summary
The corresponding cis-1,2-diols can be made
directly from alkenes by hydroxylation with OsO4
Alkenes react with divalent substances called
carbenes, to give cyclopropanes
Nonhalogenated cyclopropanes are best
prepared by a process called the Simmons
Smith reaction
Alkene polymers are formed by chain-reaction
polymerization of simple alkenes
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