Ch09-Addtn RXN and Alkenes

Organic Chemistry
Second Edition
David Klein
Chapter 9
Addition Reactions and Alkenes
Copyright © 2015 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry 2e
9.1 Addition Reactions
• Addition is
the
opposite
of
elimination
• A pi bond
is
converted
to a sigma
bond
Copyright © 2015 John Wiley & Sons, Inc. All rights reserved. 9-2 Klein, Organic Chemistry 2e
9.1 Addition Reactions
• A pi bond will often act as a Lewis base (as a
nucleophile or as a Brønsted-Lowry base)
• Why are pi bonds more reactive in this sense than

sigma bonds?
9.2 Addition / Elimination
Equilibria
• Because an addition is the reverse of an
elimination, often the processes are at equilibrium
• An equilibrium is a thermodynamic expression

• We assess ΔG (the free energy) to determine which
side the equilibrium will favor
Equilibria
• To determine which side the equilibrium will favor,

we must consider both enthalpy and entropy
Equilibria
Bonds broken – bonds formed = 166 kcal/mol – 185 kcal/mol = –19 kcal/mol
• Typical addition reactions have a –ΔH. WHY?

Equilibria
• Typical addition reactions have a –ΔH
• Will heat be absorbed by or released into the
surroundings?
• What will the sign (+/-) be for ΔSsurr?
• Will the enthalpy term favor the reactants or
products?
• The heat change (ΔH) will remain roughly constant
regardless of temperature
Equilibria
• Having a –ΔH (or a +ΔSsurr) favors the addition
reaction rather than the elimination reaction
• To get ΔG (or ΔStot) and make a complete
assessment, we must also consider the entropy of
the system (ΔSsys)
• What will the sign (+/-) be for ΔSsys? WHY?
• What will the sign (+/-) be for -TΔSsys?
• Will the enthalpy term favor the reactants or
products?
Equilibria
• Plugging into the formula gives…
• To favor addition, a –ΔG (or a +ΔStot) is needed

• How can the temperature be adjusted to favor
addition?
• To favor elimination (the reverse reaction in this
example), a +ΔG (or a –ΔStot) is needed
• How can the temperature be adjusted to favor
elimination?
9.3 Hydrohalogenation
• Note the temperature used in this addition reaction
• Does it matter whether the Br adds to the right side

of the C=C double bond or whether it adds to the
left?
• Regiochemistry becomes important for
asymmetrical alkenes
• In 1869, Markovnikov showed that in general, H

atoms tend to add to the carbon already bearing
more H atoms
• Markovnikov’s rule could also be stated by saying
that in general, halogen atoms tend to add to the
carbon that is more substituted with other carbon
groups
• This is a regioselective reaction, because one

constitutional isomer is formed in greater quantity
than another
• Draw the structure of the minor product
• Anti-Markovnikov products are observed when
reactions are performed in the presence of
peroxides such as H2O2
• Why would some reactions follow Markovnikov’s

rule, while other reactions give Anti-Markovnikov
products?
• The answer must be found in the mechanism
• Practice with conceptual9-13
checkpoint 9.1
Klein, Organic Chemistry 2e
Copyright © 2015 John Wiley & Sons, Inc. All rights reserved.
Mechanism
• The mechanism is a two step process

• Which step do you think is rate determining?
• Write a rate law for the reaction
Mechanism
• Explain the
FREE
energy
changes in
each step
Mechanism
• Recall that there are two possible products,
Markovnikov and anti-Markovnikiv
• Which process looks more favorable? WHY?

Mechanism
• Practice with SkillBuilder
9.1
9.3 Stereochemical Aspects
• In many addition reactions, chirality centers are
formed
• There are two possible Markovnikov products
• Which step in the mechanism determines the

stereochemistry of the product?
9.3 Stereochemical Aspects
• Recall the geometry of the
carbocation

checkpoint
Copyright © 2015 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry 2e
9.3 Rearrangements
• Rearrangements (hydride or methyl shifts) occur for
the carbocation if the shift makes it more stable
9.3 Rearrangements
• A mixture of products limits synthetic utility

• With an INTRAmolecular rearrangement, WHY isn’t
the rearrangement product an even greater
percentage?
• How might [Cl-] be used to alter the ratio of
products?
9.3 Hydrohalogenation Example
• Predict the major product(s) for the reaction below
9.4 Hydration
• The components of water (-H and –OH) are added
across a C=C double bond
• The acid catalyst is often shown over the arrow,

because it is regenerated rather than being a
reactant
9.4 Hydration
• Given the data below, do you think the acid
catalyzed hydration goes through a mechanism that
involves a carbocation?
9.4 Hydration Mechanism
• Why does the hydrogen add to this carbon of the

alkene?
• Mechanism continues on next slide
9.4 Hydration Mechanism
• Could a stronger base help promote the last step?

• Practice with conceptual checkpoint 9.10
9.4 Hydration Thermodynamics
• Similar to Hydrohalogenation, hydration reactions
are also at equilibrium
Addition
Elimination
• Explain HOW and WHY temperature could be used

to shift the equilibrium to the right or left
• How could Le Châtelier’s principle be used to shift

the equilibrium to the right or left?
• Similar to Hydrohalogenation, the stereochemistry
of hydration reactions is controlled by the geometry
of the carbocation
• Draw the complete mechanism for the reaction

above to show WHY a racemic mixture is formed
• Practice with SkillBuilder 9.3
9.4 Hydrations
• Ethanol is mostly produced from fermentation of
sugar using yeast, but industrial synthesis is also
used to produce ethanol through a hydration
reaction
9.5 Oxymercuration-
Demercuration
• Because rearrangements often produce a mixture
of products, the synthetic utility of Markovnikov
hydration reactions is somewhat limited
• Oxymercuration-demercuration is an alternative
process that can yeild Markovnikov products
without the possibility of rearrangement
9.5 Oxymercuration-
Demercuration
• Oxymercuration begins with mercuric acetate
• How would you classify the mercuric cation?

– As a nucleophile or an electrophile?
– As a Lewis acid or Lewis base?
• How might an alkene react with the mercuric
cation?
9.5 Oxymercuration-
Demercuration
• Similar to how we saw the alkene attack a proton
previously, it can also attack the mercuric cation
• Resonance stabilizes the mercurinium ion and the

carbocation. Draw a reasonable resonance
hybrid
9.5 Oxymercuration-
Demercuration
• The mercurinium ion is also a good electrophile,
and it can easily be attacked by a nucleophile, even
a weak nucleophile such as water
• NaBH4 is generally used to replace the –HgOAc

group with a –H group via a free radical mechanism
9.6 Hydroboration-Oxidation
• To achieve anti-Markovnikov hydration,
Hydroboration-Oxidation is often used
• Note that the process occurs in two steps
• Hydroboration-Oxidation reactions achieve syn
addition
• Anti addition is NOT observed
• To answer WHY, we must investigate the

mechanism
• Let’s examine how this new set of reagents might
react
• The BH3 molecule is similar to a carbocation but
not as reactive, because it does not carry a formal
charge
• Because of their broken octet, BH3 molecules
undergo intermolecular resonance to help fulfill
their octets
• The hybrid that results from the resonance

(diborane) involves a new type of bonding called
banana bonds
• In the hydroboration reaction, BH3•THF is used.
BH3•THF is formed when borane is stabilized with
THF (tetrahydrofuran)
• What general role do you

think BH3•THF is likely to play
in a reaction?
Hydroboration
• Let’s examine the first step of the Hydroboration

mechanism on the next slide
• What evidence is there for a concerted addition of

the B-H bond across the C=C double bond?
• Use sterics and electronics to explain the
regioselectivity of the reaction
Oxidation
Oxidation
Star
t
Her
e
• When ONE chirality center is formed, a racemic
mixture results
• WHY? What is the geometry of the alkene as the

borane attacks?
• The squiggle bond above shows two products, a
50/50 mixture of the R and the S enantiomer
• When TWO chirality centers are formed, a racemic
mixture results
• Why aren’t the other stereoisomers formed?
• Predict the major product(s) for the reactions below
9.7 Catalytic Hydrogenation
• The addition of H2 across a C=C double bond
• If a chirality center is formed, syn addition is

observed
• Draw the
stereoisomers that are
produced
• Analyze the energy diagram below
• Why is a catalyst
necessary?
• Does the catalyst affect
the spontaneity of the
process?
• Typical catalysts
include Pt, Pd, and Ni
• The metal catalyst is believed to both adsorb the H
atoms and coordinate the alkene
• The H atoms add to the same side of the alkene pi

system
• Draw product(s) for the reaction below. Pay close
attention to stereochemistry
• How many chirality centers are there in the alkene

reactant above?
• How does the term, mesocompound, describe the
product(s) of the reaction?
• If catalysis takes place on the surface of a solid
surrounded by solution, the catalyst is
heterogeneous. WHY?
• Homogeneous catalysts also exist
• What advantage might a homogeneous catalyst

have?
9.7 Asymmetric Hydrogenation
• In 1968, Knowles modified Wilkinson’s
catalyst by using a chiral phosphine
ligand
• A chiral catalyst can produce one desired

enantiomer over another. HOW?
• Why would someone want to synthesize one
enantiomer rather than a racemic mixture?
• A chiral catalyst
allows one
enantiomer to be
formed more
frequently in the
reaction mixture
• Some chiral catalysts
give better
enantioselectivity than
others. WHY?
• BINAP is a chiral ligand that gives pronounced
enantioselectivity
• For any reaction, stereoselectivity can only be

achieved if at least one reagent (reactant or
catalyst) is chiral
9.8 Halogenation
• Halogenation involves adding two halogen atoms
• Halogenation is a key step in the production of PVC
9.8 Halogenation
• Halogenation with Cl2 and Br2 is generally effective,
but halogenation with I2 is too slow and
halogenation with F2 is too violent
• Halogenation occurs with anti addition
• Given the stereospecificity, is it likely to be a

concerted or a multi-step process?
9.8 Halogenation
• Let’s look at the reactivity of Br2. Cl2 is similar
• It is nonpolar, but it is polarizable. WHY?
• What type of
attraction
exists between
the Nuc:1- and
Br2?
• Does the Br2
molecule have
a good leaving
group attached
to it?
9.8 Halogenation
• We know alkenes can act as nucleophiles
• Imagine an alkene attacking Br2. You might imagine
the formation of a carbocation
• However, this mechanism

DOES NOT match the
stereospecificity of the
reaction. HOW? WHY?
9.8 Halogenation
• Mechanism continued on next slide
9.8 Halogenation
• Only anti addition is observed. WHY?

• Prove to yourself that the products are enantiomers
rather than identical
9.8 Halogenation
• Only anti addition is observed
• Can you design a synthesis for ?
9.8 Halogenation
9.8 Halohydrin Formation
• Halohydrins are formed when halogens (Cl2 or Br2)
are added to an alkene with WATER as the solvent
• The bromonium ion forms from Br2 + alkene, and
then it is attacked by water
• Why is the bromonium attacked by water rather

than a Br1- ion? Is water a better nucleophile?
9.8 Halohydrin Formation
• A proton transfer completes the mechanism
producing a neutral halohydrin product
• The net reaction is the addition of –X and –OH

9.8 Halohydrin Regioselectivity
• The –OH group adds to the more substituted
carbon
• The key step that determines regioselectivity is the

attack of water on the bromonium ion
• When water attacks the bromonium ion, it will
attack the side that goes through the lower energy
transition state
Transition state
• Water is a small molecule that can easily access
the more sterically hindered site
9.9 Anti Dihydroxylation
• Dihydroxylation occurs when two –OH groups are
added across a C=C double bond
• Anti dihydroxylation is achieved through a multi-

step process
• First, an epoxide is formed
• Replacing the relatively unstable O-O single bond

is the thermodynamic driving force for this process
• Is there anything unstable about an epoxide?
• Is an epoxide likely to react as a nucleophile (Lewis
base) or as an electrophile (Lewis acid)?
• Water is a
poor
nucleophile
, so the
epoxide is
activated
with an
acid
• Note the similarities between three key
intermediates
• Ring strain and a +1 formal charge makes these

structures GREAT electrophiles
• They also each yield anti products, because the
nucleophile must attack from the side opposite the
leaving group
9-72 Klein, Organic Chemistry 2e
9.10 Syn Dihydroxylation
• Like other syn additions, syn dihydroxylation adds
across the C=C double bond in ONE step
• Because OsO4 is expensive and toxic, conditions
have been developed where the OsO4 is
regenerated after reacting, so only catalytic
amounts are needed
• MnO41- is similar to OsO4 but more reactive
• Syn dihydroxylation can be achieved with KMnO4
but only under mild conditions (cold temperatures)
• Diols are often further oxidized by MnO41-, and

MnO41- is reactive toward many other functional
groups as well
• The synthetic utility of MnO41- is limited
checkpoint 9.33
Klein, Organic Chemistry 2e
9.11 Oxidative Cleavage with O3
• C=C double bonds are also reactive toward
oxidative cleavage
• Ozonolysis is one such process
• Ozone exists as a resonance hybrid of two

contributors
• Common reducing agents include dimethyl sulfide

and Zn/H2O. Practice with SkillBuilder 9.8
• Predict a bicyclic reactant used to form the product

below
9.12 Predicting Addition Products
1. Analyze the reagents used to determine what
groups will be added across the C=C double bond
2. Determine the regioselectivity (Markovnikov or
anti-Markovnikov)
3. Determine the stereospecificity (syn or anti
addition)
• Each step can be achieved with minor reagent
memorization and a firm grasp of the mechanistic
rational
• The more familiar you are with the mechanisms,
the easier predicting products will be
• Practice with SkillBuilder
9-79
9.9 Klein, Organic Chemistry 2e
9.12 Predicting Addition Products
9.13 One Step Syntheses
• To set up a synthesis, assess the reactants and
products to see what changes need to be made
• Label each of the processes below
9.13 One Step Syntheses
• To set up a synthesis, assess the reactants and
products to see what changes need to be made
• Give reagents and conditions for the following
9.13 Multi-Step Syntheses
• Multistep syntheses are more challenging, but the
same strategy applies
• This is not a simple substitution, addition or

elimination, so two processes must be combined
• For the strategy to work, the regioselectivty must

be correct
• A smaller
base should
be used to
produce the
more stable
Zaitsev
product
• For the strategy to work, the regioselectivty must

be correct
• Will the
regioselectivity for
the HBr reaction
give the desired
product?
• Multistep syntheses are more challenging, but the
same strategy applies
• This is not a simple substitution, addition or

elimination, so two processes must be combined
• How can the alcohol be eliminated to give the less
stable Hoffmann product?
• H3O+ will give the Zaitsev product

• OH- is too poor of a leaving group to use the bulky
base, t-BuOK
• The OH must first be converted to a better leaving
group, and then t-BuOK can be used
• In the last step, –H and –OH must be added

across the C=C double bond
• Is the desired addition Markovnikov or anti-

Markovnikov?
• Use reagents that give anti-Markovnikov products
• Is stereochemistry an issue in this specific

reaction?

• Solve the multistep syntheses below
• Again, two processes must be combined
• What reagents should be used?

Additional Practice Problems
• If you want to favor addition rather than
elimination, do you generally want a high or low
temperature, and why?
• Predict the major product for the addition reaction
below. Be aware of possible rearrangements and
stereochemical concerns.
• How and why will the concentration of acid affect
whether an acid catalyzed hydration will favor
products or reactants at equilibrium?
• Give an example reaction for Markovnikov
hydration without the possibility of rearrangement.
• Give an example reaction for syn antiMarkovnikov

hydration.
• Should a halogenation reaction be overall first or
second order kinetics? Also, Explain why it gives
anti addition rather than syn.
• What reagents are necessary to achieve the
following synthesis?

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Organic Chemistry

• Why are pi bonds more reactive in this sense than

• An equilibrium is a thermodynamic expression

• To determine which side the equilibrium will favor,

• Typical addition reactions have a –ΔH. WHY?

• To favor addition, a –ΔG (or a +ΔStot) is needed

• Does it matter whether the Br adds to the right side

• In 1869, Markovnikov showed that in general, H

• This is a regioselective reaction, because one

• Why would some reactions follow Markovnikov’s

• The mechanism is a two step process

• Which process looks more favorable? WHY?

• There are two possible Markovnikov products

• Which step in the mechanism determines the

• Practice with conceptual9-19

• A mixture of products limits synthetic utility

• The acid catalyst is often shown over the arrow,

• Why does the hydrogen add to this carbon of the

• Could a stronger base help promote the last step?

• Explain HOW and WHY temperature could be used

• How could Le Châtelier’s principle be used to shift

• Draw the complete mechanism for the reaction

• Predict the major product(s) for the reaction below

• How would you classify the mercuric cation?

• Resonance stabilizes the mercurinium ion and the

• NaBH4 is generally used to replace the –HgOAc

• Note that the process occurs in two steps

• Anti addition is NOT observed

• To answer WHY, we must investigate the

• The hybrid that results from the resonance

• What general role do you

• Let’s examine the first step of the Hydroboration

• What evidence is there for a concerted addition of

• WHY? What is the geometry of the alkene as the

• Why aren’t the other stereoisomers formed?

• Practice with SkillBuilder 9.4

• If a chirality center is formed, syn addition is

• The H atoms add to the same side of the alkene pi

• How many chirality centers are there in the alkene

• What advantage might a homogeneous catalyst

• A chiral catalyst can produce one desired

• For any reaction, stereoselectivity can only be

• Halogenation is a key step in the production of PVC

• Given the stereospecificity, is it likely to be a

• However, this mechanism

• Mechanism continued on next slide

• Only anti addition is observed. WHY?

• Can you design a synthesis for ?

• Practice with conceptual checkpoint 9.26

• Why is the bromonium attacked by water rather

• The net reaction is the addition of –X and –OH

• The key step that determines regioselectivity is the

• Anti dihydroxylation is achieved through a multi-

• Replacing the relatively unstable O-O single bond

• Ring strain and a +1 formal charge makes these

• Diols are often further oxidized by MnO41-, and

• Ozone exists as a resonance hybrid of two

• Common reducing agents include dimethyl sulfide

• Predict a bicyclic reactant used to form the product

• Practice with SkillBuilder 9.10

• This is not a simple substitution, addition or

• For the strategy to work, the regioselectivty must

• For the strategy to work, the regioselectivty must