Alkenes: Reactions and

Synthesis

Prof. Dr. Mine Yarım Yüksel

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 :CH2)

2
Preparation of Alkenes: A Preview of
Elimination Reactions

3
Preparation of Alkenes: A Preview of
Elimination Reactions
◼ Alkenes are commonly made by
◼ elimination of HX from alkyl halide
(dehydrohalogenation)
◼ Uses heat and KOH (require strong bases)

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

◼ require strong acids (sulfuric acid, 50 ºC)

4
Addition of Halogens to Alkenes
◼ Bromine and chlorine add to alkenes to give 1,2-dihaldes,
an industrially important process
◼ F2 is too reactive, hard to control the reaction and I2
does not add
◼ Cl2 reacts as Cl+ Cl-
◼ Br2 is similar

5
Addition of Br2 to Cyclopentene
◼ Addition is exclusively trans

6
Mechanism of Bromine Addition
◼ Br+ adds to an alkene producing a cyclic ion
◼ Bromonium ion, bromine shares charge with carbon
◼ Gives trans addition

7
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

8
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

9
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)

10
11
Mechanism of Formation of a
Bromohydrin
◼ Br2 forms bromonium ion, then water adds
◼ Orientation toward stable C+ species
◼ Aromatic rings do not react

12
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

13
Addition of Water to Alkenes:
◼ 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

14
15
 Oxymercuration Intermediates (Lab
scale preparation)
◼ For laboratory-scale hydration of an alkene
◼ Use mercuric acetate in THF followed by sodium borohydride
◼ Markovnikov orientation
◼ via mercurinium ion

16
17
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

18
BH3 Is a Lewis Acid
◼ Six electrons in outer shell
◼ Coordinates to oxygen electron pairs in ethers

19
 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

20
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)

21
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

22
Hydroboration: Orientation in
Addition Step
◼ Addition in least crowded orientation, syn
◼ Addition also is via most stable carbocation

23
Hydroboration, Electronic Effects Give
Non-Markovnikov
◼ More stable carbocation is also consistent with steric
preferences

24
Hydroboration - Oxygen Insertion
Step
◼ H2O2, OH- inserts OH in place of B
◼ Retains syn orientation

25
26
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

27
Formation of Dichlorocarbene
◼ Base removes proton
from chloroform
◼ Stabilized carbanion
remains
◼ Unimolecular
Elimination of Cl- gives
electron deficient
species,
dichlorocarbene

28
Reaction of Dichlorocarbene
◼ Addition of dichlorocarbene is stereospecific cis

29
Simmons-Smith Reaction
◼ Equivalent of addition of CH2:
◼ Reaction of diiodomethane with zinc-copper alloy
produces a carbenoid species
◼ Forms cyclopropanes by cycloaddition

30
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)

31
Mechanism of Catalytic
Hydrogenation
◼ Heterogeneous – reaction between phases
◼ Addition of H-H is syn

32
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

33
34
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)

35
Osmium Tetroxide Catalyzed Formation
of Diols
◼ Hydroxylation - converts to syn-diol
◼ Osmium tetroxide, then sodium bisulfate
◼ Via cyclic osmate di-ester

36
Alkene Cleavage: Ozone
◼ Ozone, O3, adds to alkenes to form molozonide
◼ Reduce molozonide to obtain ketones and/or aldehydes

37
Examples of Ozonolysis of Alkenes
◼ Used in determination of structure of an unknown alkene

38
Structure Elucidation With Ozone
◼ Cleavage products reveal an alkene’s structure

39
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

40
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

41
Mechanism of Periodic Acid
Oxidation
◼ Via cyclic periodate intermediate

42
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

43
Biological Hydration Example
◼ Fumarate to malate catalyzed by fumarase
◼ Specific for trans isomer
◼ Addition of H, OH is anti

44
Addition of Radicals to Alkenes:
Polymers
◼ A polymer is a very large molecule consisting of repeating
units of simpler molecules (monomers), formed by
polymerization
◼ Alkenes react with radical catalysts to undergo radical
polymerization
◼ Ethylene is polymerized to poyethylene, for example

45
Free Radical Polymerization of
Alkenes
◼ Alkenes combine many times to give polymer
◼ Reactivity induced by formation of free radicals

46
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

47
Polymerization: Propagation

◼ Radical from intiation adds to alkene to generate alkene

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

48
Polymerization: Termination
◼ Chain propagation ends when two radical chains combine
◼ Not controlled specifically but affected by reactivity and
concentration

49
Other Polymers
◼ Other alkenes give other common polymers

50
51