7.

Alkenes: Reactions and

Synthesis

Based on McMurry’s Organic Chemistry, 6th edition

©2003 Ronald Kluger
Department of Chemistry
University of Toronto
Diverse Reactions of Alkenes
 Alkenes react with many electrophiles to give useful
products by addition (often through special reagents)
 alcohols (add H-OH)
 alkanes (add H-H)
 halohydrins (add HO-X)
 dihalides (add X-X)
 halides (add H-X)
 diols (add HO-OH)
 cyclopropane (add :CH )
2

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7.1 Preparation of Alkenes: A Preview of
Elimination Reactions
 Alkenes are commonly made by
 elimination of HX from alkyl halide
(dehydrohalogenation)
 Uses heat and KOH

 elimination of H-OH from an alcohol (dehydration)

 require strong acids (sulfuric acid, 50 ºC)

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7.2 Addition of Halogens to Alkenes
 Bromine and chlorine add to alkenes to give 1,2-dihaldes,
an industrially important process
 F2 is too reactive and I2 does not add

 Cl2 reacts as Cl+ Cl-

 Br2 is similar

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Addition of Br2 to Cyclopentene
 Addition is exclusively trans

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Mechanism of Bromine Addition
 Br+ adds to an alkene producing a cyclic ion
 Bromonium ion, bromine shares charge with carbon
 Gives trans addition

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Bromonium Ion Mechanism
 Electrophilic addition of
bromine to give a cation is
followed by cyclization to
give a bromonium ion
 This bromoniun ion is a
reactive electrophile and
bromide ion is a good
nucleophile

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The Reality of Bromonium Ions
 Bromonium were postulated more than 60 years ago to
expain the stereochemical course of the addition (to give
the trans-dibromide from a cyclic alkene
 Olah showed that bromonium ions are stable in liquid SO2
with SbF5 and can be studied directly

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7.3 Halohydrin Formation
 This is formally the addition of HO-X to an alkene (with
+
OH as the electrophile) to give a 1,2-halo alcohol, called a
halohydrin
 The actual reagent is the dihalogen (Br2 or Cl2 in water in
an organic solvent)

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Mechanism of Formation of a
Bromohydrin
 Br2 forms bromonium ion, then water adds
 Orientation toward stable C+ species
 Aromatic rings do not react

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An Alternative to Bromine
 Bromine is a difficult reagent to use for this reaction
 N-Bromosuccinimide (NBS) produces bromine in organic
solvents and is a safer source

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7.4 Addition of Water to Alkenes:
Oxymercuration
 Hydration of an alkene is the addition of H-OH to to give
an alcohol
 Acid catalysts are used in high temperature industrial
processes: ethylene is converted to ethanol

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 Oxymercuration Intermediates
 For laboratory-scale hydration of an
alkene
 Use mercuric acetate in THF followed
by sodium borohydride
 Markovnikov orientation
 via mercurinium ion

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7.5 Addition of Water to Alkenes:
Hydroboration
 Herbert Brown (HB) invented hydroboration (HB)
 Borane (BH3) is electron deficient is a Lewis acid
 Borane adds to an alkene to give an organoborane

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BH3 Is a Lewis Acid
 Six electrons in outer shell
 Coordinates to oxygen electron pairs in ethers

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 Hydroboration-Oxidation Forms an
Alcohol from an Alkene
 Addition of H-BH2 (from BH3-THF complex) to three alkenes
gives a trialkylborane
 Oxidation with alkaline hydrogen peroxide in water produces
the alcohol derived from the alkene

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Orientation in Hydration via
Hydroboration
 Regiochemistry is opposite to Markovnikov orientation
 OH is added to carbon with most H’s
 H and OH add with syn stereochemistry, to the same
face of the alkene (opposite of anti addition)

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Mechanism of Hydroboration
 Borane is a Lewis acid
 Alkene is Lewis base
 Transition state involves
anionic development on B
 The components of BH3
are across C=C

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Hydroboration: Orientation in
Addition Step
 Addition in least crowded orientation, syn
 Addition also is via most stable carbocation

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Hydroboration, Electronic Effects Give
Non-Markovnikov
 More stable carbocation is also consistent with steric
preferences

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Hydroboration - Oxygen Insertion
Step
 H2O2, OH- inserts OH in place of B
 Retains syn orientation

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7.6 Addition of Carbenes to Alkenes
 The carbene functional group is “half of an alkene”
 Carbenes are electrically neutral with six electrons in the
outer shell
 They symmetrically across double bonds to form
cyclopropanes

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Formation of Dichlorocarbene
 Base removes proton
from chloroform
 Stabilized carbanion
remains
 Unimolecular
Elimination of Cl- gives
electron deficient
species,
dichlorocarbene

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Simmons-Smith Reaction
 Equivalent of addition of CH2:
 Reaction of diiodomethane with zinc-copper alloy produces
a carbenoid species
 Forms cyclopropanes by cycloaddition

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Reaction of Dichlorocarbene
 Addition of dichlorocarbene is stereospecific cis

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7.7 Reduction of Alkenes:
Hydrogenation
 Addition of H-H across C=C
 Reduction in general is addition of H2 or its equivalent
 Requires Pt or Pd as powders on carbon and H2
 Hydrogen is first adsorbed on catalyst
 Reaction is heterogeneous (process is not in solution)

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Hydrogen Addition- Selectivity
 Selective for C=C. No reaction with C=O,
C=N
 Polyunsaturated liquid oils become solids
 If one side is blocked, hydrogen adds to other

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Mechanism of Catalytic
Hydrogenation
 Heterogeneous – reaction between phases
 Addition of H-H is syn

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7.8 Oxidation of Alkenes:
Hydroxylation and Cleavage
 Hydroxylation adds OH to each end of C=C
 Catalyzed by osmium tetroxide
 Stereochemistry of addition is syn
 Product is a 1,2-dialcohol or diol (also called a glycol)

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Osmium Tetroxide Catalyzed Formation
of Diols
 Hydroxylation - converts to syn-diol
 Osmium tetroxide, then sodium bisulfate
 Via cyclic osmate di-ester

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Alkene Cleavage: Ozone
 Ozone, O3, adds to alkenes to form molozonide
 Reduce molozonide to obtain ketones and/or aldehydes

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Examples of Ozonolysis of Alkenes
 Used in determination of structure of an unknown alkene

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Structure Elucidation With Ozone
 Cleavage products reveal an alkene’s structure

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Permangante Oxidation of Alkenes
 Oxidizing reagents other than ozone also cleave alkenes
 Potassium permanganate (KMnO4) can produce carboxylic
acids and carbon dioxide if H’s are present on C=C

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Cleavage of 1,2-diols
 Reaction of a 1,2-diol with periodic (per-iodic) acid, HIO4 ,
cleaves the diol into two carbonyl compinds
 Sequence of diol formation with OsO4 followed by diol
cleavage is a good alternative to ozonolysis

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Mechanism of Periodic Acid
Oxidation
 Via cyclic periodate intermediate

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7.9 Biological Alkene Addition
Reactions
 Living organisms convert organic molecules using
enzymes as catalysts
 Many reactions are similar to organic chemistry
conversions, except they occur in neutral water
 Usually much specific for reactant and stereochemistry

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Biological Hydration Example
 Fumarate to malate catalyzed by fumarase
 Specific for trans isomer
 Addition of H, OH is anti

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7.10 Addition of Radicals to Alkenes:
Polymers
 A polymer is a very large molecule consisting of repeating
units of simpler molecules, formed by polymerization
 Alkenes react with radical catalysts to undergo radical
polymerization
 Ethylene is polymerized to poyethylene, for example

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Free Radical Polymerization of
Alkenes
 Alkenes combine many times to give polymer
 Reactivity induced by formation of free radicals

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Free Radical Polymerization:
Initiation
 Initiation - a few radicals are generated by the reaction of
a molecule that readily forms radicals from a nonradical
molecule
 A bond is broken homolytically

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Polymerization: Propagation

 Radical from intiation adds to alkene to generate alkene

derived radical
 This radical adds to another alkene, and so on many times

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Polymerization: Termination
 Chain propagation ends when two radical chains combine
 Not controlled specifically but affected by reactivity and
concentration

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Other Polymers
 Other alkenes give other common polymers

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Unsymmetrical Monomers
 If alkene is unsymmetrical, reaction is via more highly
substituted radical

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Chain Branching During
Polymerization
 During radical propagation chain can develop forks leading
to branching
 One mechanism of branching is short chain branching in
which an internal hydrogen is abstracted

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Long Chain Branching
 In long chains, a hydrogen from another chain is
abstracted

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Cationic Polymerization
 Vinyl monomers react with Brønsted or Lewis
acid to produce a reactive carbocation that
adds to alkenes and propagates via
lengthening carbocations

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