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8. Alkenes: Reactions and 8. Alkenes: Reactions and SynthesisSynthesis
Why this chapter?Why this chapter?
To begin a systematic description of major functional groupsBegin to focus on general principles and patterns of reactivity that tie organic chemistry
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Diverse Reactions of AlkenesDiverse Reactions of Alkenes Alkenes react with many electrophiles to give useful
products by addition (often through special reagents)
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8.1 Preparation of Alkenes: A Preview of 8.1 Preparation of Alkenes: A Preview of Elimination ReactionsElimination 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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Preview of Elimination ReactionsPreview of Elimination Reactions
Dehydrohalogenation: Loss of HX
With and strong base (KOH)
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Preview of Elimination ReactionsPreview of Elimination Reactions
Dehydration: Loss of HOH With strong acid cat (H2SO4)
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8.2 Addition of Halogens to Alkenes8.2 Addition of Halogens to AlkenesBromine 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 BrAddition of Br22 to Cyclopentene to Cyclopentene Addition is exclusively trans
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Mechanism of Bromine AdditionMechanism of Bromine AdditionBr+ adds to an alkene producing a cyclic ionBromonium ion, bromine shares charge with carbon
◦ Gives trans addition
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Bromonium Ion MechanismBromonium 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 IonsThe Reality of Bromonium Ions Bromonium ions were postulated more than 60 years ago to
explain 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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p. 218
Biological HalogenationBiological Halogenation•Occurs in marine organisms.•“Br1+” or “Cl1+” like compounds made by oxidizing Br1- or Cl1- with H2O2
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Which product will result from the following Which product will result from the following reaction? reaction?
1. 2.
3. 4. 5.
Cl2
CH2Cl2
Learning Check:Learning Check:
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Which product will result from the following Which product will result from the following reaction? reaction?
1. 2.
3. 4. 5.
Cl2
CH2Cl2
Solution:Solution:
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8.3 Addition of Hypohalous Acids to Alkenes: 8.3 Addition of Hypohalous Acids to Alkenes: Halohydrin FormationHalohydrin Formation
This is formally the addition of HO-X to an alkene 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 BromohydrinMechanism 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 BromineAn Alternative to BromineBromine is a difficult reagent to use for this reactionN-Bromosuccinimide (NBS) produces bromine in
organic solvents and is a safer source
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Which of the compounds will result from the Which of the compounds will result from the reaction of NBS/Hreaction of NBS/H22O/DMSO with 1-O/DMSO with 1-methylcyclopentene?methylcyclopentene?
1. 2.
3. 4. 5.
Learning Check:Learning Check:
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Which of the compounds will result from the Which of the compounds will result from the reaction of NBS/Hreaction of NBS/H22O/DMSO with 1-O/DMSO with 1-methylcyclopentene?methylcyclopentene?
1. 2.
3. 4. 5.
Solution:Solution:
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8.4 Addition of Water to Alkenes:8.4 Addition of Water to Alkenes:Hydration of an alkene is the addition of H-OH to to
give an alcoholAcid catalysts are used in high temperature industrial
processes: ethylene is converted to ethanol
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Fig. 7-2, p. 221
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p. 222
Biological Addition of WaterBiological Addition of Water
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p. 222
OxymercurationOxymercuration
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Oxymercuration IntermediatesOxymercuration IntermediatesFor laboratory-scale hydration of an alkeneUse mercuric acetate in THF followed by sodium
borohydrideMarkovnikov orientation
◦ via mercurinium ion
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8.5 Addition of Water to Alkenes: 8.5 Addition of Water to Alkenes: HydroborationHydroboration
Herbert Brown (HB) invented hydroboration (HB)Borane (BH3) is electron deficient is a Lewis acidBorane adds to an alkene to give an organoborane
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p. 223
BHBH33-THF Complex-THF Complex
THF = Tetrahydrofuran; a common ether solvent
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Addition of H-BH2 (from BH3-THF complex) to three
alkenes gives a trialkylboraneOxidation with alkaline hydrogen peroxide in water
produces the alcohol derived from the alkene
Hydroboration-Oxidation: Alkene Alcohol
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Orientation in Hydration via HydroborationOrientation in Hydration via HydroborationRegiochemistry 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 HydroborationMechanism of Hydroboration Borane is a Lewis acid Alkene is Lewis base Transition state involves anionic development on B The components of BH3 are added across C=C
More stable carbocation is consistent with steric preferences
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p. 225
Example:Example:
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p. 225
Learning CheckLearning Check
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p. 226
Solution:Solution:Options are:
So:
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8.6 Reduction of Alkenes: Hydrogenation8.6 Reduction of Alkenes: HydrogenationAddition of H-H across C=CReduction in general is addition of H2 or its equivalent Requires Pt or Pd as powders on carbon and H2
Hydrogen is first adsorbed on catalystReaction is heterogeneous (process is not in solution)
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Hydrogen Addition- SelectivityHydrogen Addition- SelectivitySelective for C=C. No reaction with C=O, C=NPolyunsaturated liquid oils become solidsIf one side is blocked, hydrogen adds to other
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Mechanism of Catalytic HydrogenationMechanism of Catalytic HydrogenationHeterogeneous
– reaction between phases
Addition of H-H is syn
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p. 232
Examples:Examples:
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p. 232
Examples:Examples:
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p. 232
Learning Check:Learning Check:What product would you obtain from catalytic hydrogenation of the following alkenes?
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Fig. 7-8, p. 233
Biological Example:Biological Example:
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Which compound is Which compound is the bestthe best starting starting material for hydrogenation to decalin material for hydrogenation to decalin shown below? shown below?
1. 2.
3. 4. 5.
H
HH2 (< 1atm)
Pd/C
?
Learning Check:Learning Check:
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Which compound is Which compound is the bestthe best starting starting material for hydrogenation to decalin material for hydrogenation to decalin shown below? shown below?
1. 2.
3. 4. 5.
H
HH2 (< 1atm)
Pd/C
?
Solution:Solution:
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8.7 Oxidation of Alkenes: 8.7 Oxidation of Alkenes: Epoxidation and HydroxylationEpoxidation and Hydroxylation
Epoxidation results in a cyclic ether with an oxygen atom
Stereochemistry of addition is syn
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p. 234
Ways to Make EpoxidesWays to Make Epoxides
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p. 234
Use Epoxides to make DiolsUse Epoxides to make Diols
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Osmium Tetroxide Catalyzed Osmium Tetroxide Catalyzed Formation of DiolsFormation of Diols
Hydroxylation - converts to syn-diolOsmium tetroxide, then sodium bisulfateVia cyclic osmate di-ester
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8.8 Oxidaton of Alkenes:8.8 Oxidaton of Alkenes:Cleavage to Carbonyl CompoundsCleavage to Carbonyl Compounds
Ozone, O3, adds to alkenes to form molozonideReduce molozonide to obtain ketones and/or
aldehydes
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Examples of Ozonolysis of AlkenesExamples of Ozonolysis of AlkenesUsed in determination of structure of an unknown alkene
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Compound X reacts with OCompound X reacts with O33 (followed by (followed by Zn/AcOH) to give I and II. Zn/AcOH) to give I and II.
Which of the following could be X?
1. 2.
3. 4. 5.
O O
O O
H
I II
Learning Check:Learning Check:
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Compound X reacts with OCompound X reacts with O33 (followed by (followed by Zn/AcOH) to give I and II. Zn/AcOH) to give I and II.
Which of the following could be X?
1. 2.
3. 4. 5.
O O
O O
H
I II
Solution:Solution:
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Permangante Oxidation of AlkenesPermangante Oxidation of AlkenesOxidizing reagents other than ozone also cleave alkenesPotassium 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-diolsCleavage of 1,2-diolsReaction of a 1,2-diol with periodic (per-iodic) acid,
HIO4 , cleaves the diol into two carbonyl compounds
Sequence of diol formation with OsO4 followed by diol cleavage is a good alternative to ozonolysis
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What is the major product of the following What is the major product of the following reaction?reaction?
1. 2.
3. 4.5.
1. OsO4
2. NaHSO3/H2O
Learning Check:Learning Check:
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What is the major product of the following What is the major product of the following reaction?reaction?
1. 2.
3. 4.5.
1. OsO4
2. NaHSO3/H2O
Solution:Solution:
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Which of the following will react with Which of the following will react with periodic acid (HIOperiodic acid (HIO44) to give an aldehyde?) to give an aldehyde?
1. 2.
3. 4. 5.
Learning Check:Learning Check:
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Which of the following will react with Which of the following will react with periodic acid (HIOperiodic acid (HIO44) to give an aldehyde?) to give an aldehyde?
1. 2.
3. 4. 5.
Solution:Solution:
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8.9 Addition of Carbenes to Alkenes8.9 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 add symmetrically across double bonds to form
cyclopropanes
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Formation of DichlorocarbeneFormation of DichlorocarbeneBase removes
proton from chloroform
Stabilized carbanion remains
Unimolecular elimination of Cl- gives electron deficient species, dichlorocarbene
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Reaction of DichlorocarbeneReaction of DichlorocarbeneAddition of dichlorocarbene is stereospecific cis
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Simmons-Smith ReactionSimmons-Smith ReactionEquivalent of addition of CH2: Reaction of diiodomethane with zinc-copper
alloy produces a carbenoid speciesForms cyclopropanes by cycloaddition
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8.10 Radical Addition to Alkenes: Polymers8.10 Radical Addition to Alkenes: Polymers A polymer is a very large molecule consisting of repeating
units of simpler molecules, formed by polymerization
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PolymersPolymers
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Free Radical Polymerization: InitiationFree 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
Alkenes react with radical catalysts to undergo radical polymerization
Ethylene is polymerized to poyethylene, for example
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Polymerization: PropagationPolymerization: PropagationRadical from initiation adds to alkene to
generate alkene derived radicalThis radical adds to another alkene, and so on
many times
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Polymerization: TerminationPolymerization: TerminationChain propagation ends when two radical chains combineNot controlled specifically but affected by reactivity and
concentration
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Other PolymersOther PolymersOther alkenes give other common polymers
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Table 7-1, p. 242
Other PolymersOther Polymers
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Which monomer would give the polymer Which monomer would give the polymer shown below?shown below?
1. 2.
3. 4. 5.
Cl Cl Cl
Learning Check:Learning Check:
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Which monomer would give the polymer Which monomer would give the polymer shown below?shown below?
1. 2.
3. 4. 5.
Cl Cl Cl
Solution:Solution:
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8.11 Biological Additions of Radicals to Alkenes8.11 Biological Additions of Radicals to Alkenes Severe limitations to the usefulness of radical addition reactions in
the lab In contrast to electrophilic additions, reactive intermediate is not
quenched so it reacts again and again uncontrollably
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Biological ReactionsBiological ReactionsBiological reactions different than in the
laboratoryOne substrate molecule at a time is
present in the active site of an enzyme Biological reactions are more controlled,
more specific than other reactions
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p. 245
Natural RubberNatural Rubber
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8.12 Stereochemistry of Reactions: 8.12 Stereochemistry of Reactions: Addition of HAddition of H22O to AlkenesO to Alkenes
Many reactions can produce new chirality centers from compounds without them
What is the stereochemistry of the chiral product?
What relative amounts of stereoisomers form?Example addition of H2O to 1-butene
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Achiral Intermediate Gives Achiral Intermediate Gives Racemic ProductRacemic Product
Addition via carbocationTop and bottom are equally accessible
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8.13 Stereochemistry of Reactions: 8.13 Stereochemistry of Reactions: Addition of HAddition of H22O to a Chiral AlkeneO to a Chiral Alkene
What is the sterochemical result of the addition of H2O to a chiral alkene R-4-methyl-1-hexene
Product has 2 chiral centers
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Fig. 9-16, p. 313
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SummarySummary
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Which sequence of reagents is necessary Which sequence of reagents is necessary to carry out the following synthesis?to carry out the following synthesis?
multiple steps OH
OH
1. Br2/hv; NaOH; RCO3H; H3O+
2. Cl2/heat; KOH; OsO4; NaHSO3/H2O
3. H2/Pd; NBS/H2O/DMSO; H3O+
4. KOH; OsO4; NaHSO3/H2O
5. NaOH; Br2/H2O; KOH; H3O+
Learning Check:Learning Check:
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Which sequence of reagents is necessary Which sequence of reagents is necessary to carry out the following synthesis?to carry out the following synthesis?
multiple steps OH
OH
1. Br2/hv; NaOH; RCO3H; H3O+
2. Cl2/heat; KOH; OsO4; NaHSO3/H2O
3. H2/Pd; NBS/H2O/DMSO; H3O+
4. KOH; OsO4; NaHSO3/H2O
5. NaOH; Br2/H2O; KOH; H3O+
Solution:Solution:
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Which alkene would produce two identical Which alkene would produce two identical ketones when reacted with KMnOketones when reacted with KMnO44/H/H++? ?
1.2.
3.
4. 5.
Learning Check:Learning Check:
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Which alkene would produce two identical Which alkene would produce two identical ketones when reacted with KMnOketones when reacted with KMnO44/H/H++? ?
1.2.
3.
4. 5.
Solution:Solution:
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What kind of intermediate is involved in What kind of intermediate is involved in the biosynthesis of prostaglandins from the biosynthesis of prostaglandins from arachidonic acid?arachidonic acid?
1. carbocations2. carbanions3. carbon-base
radicals4. bromonium ions5. carbenes
Learning Check:Learning Check:
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What kind of intermediate is involved in What kind of intermediate is involved in the biosynthesis of prostaglandins from the biosynthesis of prostaglandins from arachidonic acid?arachidonic acid?
1. carbocations2. carbanions3. carbon-base
radicals4. bromonium ions5. carbenes
Solution:Solution:
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What is the best reagent to carry What is the best reagent to carry out the following reaction? out the following reaction?
1. CH2Cl2/Zn(Cu)
2. CH2l2/Zn(Cu); Cl23. CH2Cl2/KOH
4. CHCl3/KOH
5. Cl2/H2O, CH3I/KOH
ClCl
Learning Check:Learning Check:
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What is the best reagent to carry What is the best reagent to carry out the following reaction? out the following reaction?
1. CH2Cl2/Zn(Cu)
2. CH2l2/Zn(Cu); Cl23. CH2Cl2/KOH
4. CHCl3/KOH
5. Cl2/H2O, CH3I/KOH
ClCl
Solution:Solution:
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Which of the following reactions Which of the following reactions would notwould not yield at least one alcohol functional group? yield at least one alcohol functional group?
1. hydroboration of an internal alkene, followed by H2O2/NaOH
2. reaction of a mono-substituted alkene with NBS/H2O/DMSO
3. osmium tetroxide oxidation of a tetrasubstituted cyclic alkene, followed by NaHSO3
4. oxymercuration/demercuration of terminal alkene
5. oxidative cleavage of a tetrasubstituted alkene using KMnO4/H+
Learning Check:Learning Check:
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Which of the following reactions Which of the following reactions would notwould not yield at least one alcohol functional group? yield at least one alcohol functional group?
1. hydroboration of an internal alkene, followed by H2O2/NaOH
2. reaction of a mono-substituted alkene with NBS/H2O/DMSO
3. osmium tetroxide oxidation of a tetrasubstituted cyclic alkene, followed by NaHSO3
4. oxymercuration/demercuration of terminal alkene
5. oxidative cleavage of a tetrasubstituted alkene using KMnO4/H+
Solution:Solution:
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Which of the following compounds would Which of the following compounds would yield trialkylborane shown below when yield trialkylborane shown below when treated with BHtreated with BH33/THF?/THF?
1. 2-methylbut-1-ene
2. 2-methylbut-2-ene
3. 3-methylbut-1-ene
4. 2-methylpropene5. (E)-2-pentene
B
Learning Check:Learning Check:
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Which of the following compounds would Which of the following compounds would yield trialkylborane shown below when yield trialkylborane shown below when treated with BHtreated with BH33/THF?/THF?
1. 2-methylbut-1-ene
2. 2-methylbut-2-ene
3. 3-methylbut-1-ene
4. 2-methylpropene5. (E)-2-pentene
B
Solution:Solution:
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What is the product of reaction of 1-What is the product of reaction of 1-methylcyclohexene with Hg(OAc)methylcyclohexene with Hg(OAc)22/H/H22O/THF O/THF followed by NaBDfollowed by NaBD44? (D = ? (D = 22H)H)
1. 2.
3.
4. 5.
Learning Check:Learning Check:
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What is the product of reaction of 1-What is the product of reaction of 1-methylcyclohexene with Hg(OAc)methylcyclohexene with Hg(OAc)22/H/H22O/THF O/THF followed by NaBDfollowed by NaBD44? (D = ? (D = 22H)H)
1. 2.
3.
4. 5.
Solution:Solution:
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Which reaction sequence on an alkene Which reaction sequence on an alkene will accomplish the same end result as will accomplish the same end result as treating the alkene with Otreating the alkene with O33 followed by followed by Zn/AcOH?Zn/AcOH?
1. RCO3H followed by KMnO4/H3O+
2. BH3/THF followed by OsO4 followed by NaHSO3/H2O
3. OsO4/NMO followed by HIO4
4. Hg(OAc)2/H2O/THF followed by NaBH4 followed by KOH
5. Br2/H2O followed by KOH, followed by H3O+
Learning Check:Learning Check:
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Which reaction sequence on an alkene Which reaction sequence on an alkene will accomplish the same end result as will accomplish the same end result as treating the alkene with Otreating the alkene with O33 followed by followed by Zn/AcOH?Zn/AcOH?
1. RCO3H followed by KMnO4/H3O+
2. BH3/THF followed by OsO4 followed by NaHSO3/H2O
3. OsO4/NMO followed by HIO4
4. Hg(OAc)2/H2O/THF followed by NaBH4 followed by KOH
5. Br2/H2O followed by KOH, followed by H3O+
Solution:Solution: