Chapter 8: Addition Reactions of Alkenes

Hello
 Chapter 8: Addition Reactions of Alkenes
Topics:
I. Introduction to Addition Reactions
II. Alkenes in Nature and in Industry
III. Addition vs. Elimination: A Thermodynamic Perspective
IV. Hydrohalogenation
V. Hello
Acid-Catalyzed Hydration
VI. Oxymercuration-Demercuration
VII. Hydroboration-Oxidation
VIII. Catalytic Hydrogenation
IX. Halogenation and Halohydrin Formation
X. Anti Dihydroxylation
XI. Syn Dihydroxylation
XII. Oxidative Cleavage
XIII. Predicting the Products of an Addition Reaction
XIV. Synthesis Strategies 2
 I. Introduction to Addition Reactions
• Addition is the C=C π bond is
opposite of converted to two
elimination new sigma bonds

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 I. Introduction to Addition Reactions

• The π bond is an electron-pair donor

• Remember the electrons in a π bond are located above and
below the nucleus so they are higher in potential energy.

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• A wide variety of different products can be obtained depending

upon the nucleophile or electrophile that is chosen.
II. Alkenes in Nature and Industry

• Naturally occurring, acyclic alkenes:

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II. Alkenes in Nature and Industry

• Cyclic and polycyclic alkenes:

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II. Alkenes in Nature and Industry

• C=C double bonds often found in the structures of pheromones

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II. Alkenes in Nature and Industry

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• Alkenes are critical precursors in the chemical industry

• 70 billion pounds of propylene (propene) and 200 billion pounds of

ethylene (ethene) are both made from cracking petroleum each year
II. Alkenes in Nature and Industry

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 II. Alkenes in Nature and Industry
• Alkenes are also used in polymerization reactions to make
• Polyethylene poly: many ethylene: H2C=CH2
• Polypropylene propylene: H2C=CHCH3
• Polystyrene styrene:
Hello

Polyethylene Polypropylene Polystyrene

III. Addition vs. Elimination: A Thermodynamic
Perspective
• Addition and elimination are equilibrating reactions:
– An addition reaction is simply the reverse of an elimination
reaction.
– At high temperatures, elimination is preferred
– At lower temperatures, addition is preferred
Hello
III. Addition vs. Elimination: A Thermodynamic
Perspective
• Addition reactions are favored by enthalpy. (∆H is negative)
• Sigma bonds are stronger (more stable) than π bonds

Hello

ΔH = Bonds broken – bonds formed

ΔH = 166 kcal/mol – 185 kcal/mol
ΔH = –19 kcal/mol

• We are breaking one π bond and one sigma bond to make 2 sigma
bonds
III. Addition vs. Elimination: A Thermodynamic
Perspective
• Addition reactions are NOT favored by entropy. (∆S is negative)
• Two molecules combine to form one product; entropy decreases

Hello

Two reactants ONE product

III. Addition vs. Elimination: A Thermodynamic
Perspective
• At lower temps, enthalpy dominates, and addition reactions are
favored
• At higher temps, entropy dominates, and elimination reactions are
favored
• So, we use lower temperatures when doing an addition reaction
Hello

At a low temperature, this term

small (∆H dominates), at a high
∆G = ∆H + (−T∆S) temperature, this term is large
Enthalpy Entropy and −T∆S dominates
Always NegaOve Always PosiOve
IV. Hydrohalogenation

• Hydrohalogenation: addition of H-X to an alkene

• can use HCl, HBr, or HI

Hello

• If the alkene is not symmetrical, then two regioisomers are

“possible”, depending on which carbon gets the “H” and the “X”
IV. Hydrohalogenation

• Hydrohalogenation is regioselective for Markovnikov addition

• In 1869, Markovnikov observed the H atoms tend to add to the

carbon already bearing more H atoms
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★ The halogen is generally installed at the more substituted

carbon.
IV. Hydrohalogenation

• When peroxides are used with HBr, the opposite regioselectivity

is observed.

Hello

• The reaction mechanism must be different, when peroxides are

present. (Radical Mechanism, will learn in chapter 10)
IV. Hydrohalogenation

• The important lesson here is that the regioselectivity of HBr

addition can be controlled:

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IV. Hydrohalogenation
Draw the expected major product for the following reactions

Hello
IV. Hydrohalogenation
Answer:

Hello
Markovnikov Product

Markovnikov Product
IV. Hydrohalogenation
Draw the expected major product for the following reactions

HBr
a. ROOR

Hello
b.
HCl

c. HI

d. HBr
ROOR
IV. Hydrohalogenation
Answers: If it is just HX, The H+ will add to the least substituted carbon since the positive
charge will always end up on the most substituted carbon. The X_ then the carbon bearing
the positive charge. (Don’t worry about the explanation below until after chapter 10)
With HX and ROOR, it is a bit more difficult to explain without covering radical reactions.
Basically the ROOR splits into 2RO·. This free radical then splits the H-X bond forming ROH + X·.

a. HBr The halogen radical (X·)

Br
ROOR
then reacts with the double
Hello bond leaving the radical on
the most substituted carbon
and the halogen on the
b. HCl Cl
least substituted carbon.
Finally, that radical abstracts
an H from another H-X bond
I which regenerates the X·
HI
c. species.

Br

HBr
d. ROOR
IV. Hydrohalogenation
Identify the reagents that you would use to achieve each of the
following transformations:
Br

a.

Hello
Br
b.

c. Br

Br

d.
 IV. Hydrohalogenation
Answers: If you are just adding HBr, the Br will end up on the most substituted
carbon (make sure you know why)! If you are adding HBr and ROOR, the Br will end
up on the least substituted carbon (you wont know why until chapter 10)
Br

HBr
a. ROOR

Hello
Br
HBr
b.
With example d., after adding the H+
to the double bond, the secondary
carbocation may rearrange to form
the more stable tertiary carbocation
c. HBr Br
through a 1,2 hydride shift. The Br−
ROOR
then attacks the tertiary
carbocation. Typically, a mixture of
products is observed
d. HBr
Br

Br
IV. Hydrohalogenation

• The mechanism is a two step process

Hello
IV. Hydrohalogenation

• The step with the highest Ea is the rate determining step, which is
the formation of the carbocation intermediate (the first step)

Hello
IV. Hydrohalogenation

• Recall that there are two possible products, Markovnikov and anti-
Markovnikov
2˚ carbocation
intermediate

anti Markovnikov
Hello
pathway

3˚ carbocation
intermediate

Markovnikov
pathway

• Markovnikov product is formed because of carbocation stability

IV. Hydrohalogenation

• The Markovnikov product is formed through a lower energy (i.e.

faster) transition state.

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IV. Hydrohalogenation

• Hydrohalogenation may result in the formation of a chiral center

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• There are actually TWO Markovnikov products formed in this reaction

Two enantiomers are

formed in equal
amounts
IV. Hydrohalogenation

• The carbocation intermediate can be attacked from either side of

the empty p orbital, with equal probability

Hello
IV. Hydrohalogenation
Predict the product(s) for each of the following reactions.

HBr
a.

Hello

HCl
b.

HBr
c.
 IV. Hydrohalogenation
Answers: If you form a chiral center, you will produce both products equally. A
carbocation is sp2 hybridized and planar, so attack will occur from both the top and
the bottom with equal probability. If you do not form a chiral center, then only one
product is formed.

a. HBr

Br Br
Hello

Br
HCl

b.

HBr Br Br

c.
IV. Hydrohalogenation
Predict the product(s) for each of the following reactions.

d. HI

Hello

e. HCl

HCl
f.
 IV. Hydrohalogenation
Answers: If you form a chiral center, you will produce both products equally. A
carbocation is sp2 hybridized and planar, so attack will occur from both the top and
the bottom with equal probability. If you do not form a chiral center, then only one
product is formed.

d. HI
Hello
Br
Br

e. HCl
Br

Br Br
f. HCl
IV. Hydrohalogenation

• Recall carbocations can rearrange (hydride or methyl shift) if they

can become more stable.

1,2-hydride shift
Hello

• When this alkene undergoes hydrohalogenation, the 2˚ carbocation

could rearrange to a more stable, 3˚ carbocation
IV. Hydrohalogenation

• Recall carbocations can rearrange (hydride or methyl shift) if they

can become more stable.
• When carbocation rearrangements can occur, they DO occur!

Hello
IV. Hydrohalogenation
For each reaction, predict the product(s) formed and draw a
mechanism for the reaction.

a. HBr

Hello

HBr
b.

HBr

c.
IV. Hydrohalogenation
Answers: Make sure you look for potential hydride/alkyl shifts and the
formation of chiral centers. H Br
Br

a. H Br 1,2-hydride shift
1,2-hydride shift

Br Br Br
H
Nonohydride shift
hydride shift

Hello
Br Three products formed.
b.
Br

Only product. No 1,2 shi_s and

H Br
no chiral centers formed.

Br Br Br
1,2-methyl shift
1,2-hydride shift
c.
H Br
Four products formed.
Br
No shifts Br Br
no hydride shift
V. Acid Catalyzed Hydration

• The components of water (H and OH) are added across the π bond
• Acid-catalyzed hydration follows Markovnikov regeioselectivity

Hello

• Sulfuric acid is typically the acid catalyst used

V. Acid Catalyzed Hydration

• The OH is added to the more substituted carbon of the alkene

• The more substituted the carbon atom is, the faster the reaction
(easier to form the carbocation which is the slow step)
★ Same mechanism as the last section (with HBr and HCl), however
Hello
the final step is a deprotonation step.

this data is consistent

with a mechanism
that proceeds through
a carbocation
intermediate
V. Acid Catalyzed Hydration

• The mechanism for acid-catalyzed hydration is essentially the same

as hydrohalogenation:

Hello
V. Acid Catalyzed Hydration

• The mechanism for acid-catalyzed hydration is essentially the same

as hydrohalogenation:
• But with hydration, nucleophilic attack produces an oxonium ion,
which is deprotonated to afford the alcohol product:
Hello
V. Acid Catalyzed Hydration

• The reactants and products of hydration are in equilibrium

• We exploit La Chatelier’s principle to control the equilibrium

Hello

• If we are synthesizing an alcohol from an alkene, we would use

excess water
• If we are synthesizing an alkene from an alcohol, we would only
concentrated acid, and less water to the reaction
V. Acid Catalyzed Hydration
• The stereochemistry of hydration is analogous to hydrohalogenation, for the
same reason(s).
• If a new chirality center is formed, a mixture of R and S is obtained

Hello

• As always, if enantiomers are formed in a reaction, then a racemic mixture is

obtained.
• If this doesn’t make sense, review the last section
(hydrohalogenation). If it still doesn’t make sense, see me!
• This will be a common theme, many mechanisms will repeat over
and over again. Best to understand, worse to try to memorize
each one, especially since they are so similar to one another!
V. Acid Catalyzed Hydration
In each of the following cases, identify the alkene that is expected
to be more reactive toward acid-catalyzed hydration and explain
your reasoning

Hello
a.

b. 2-methyl-2-butene 3-methyl-1-butene
V. Acid Catalyzed Hydration
Answers: The most reactive alkene will produce the most stable
carbocation. Remember, tertiary(3°) is the most stable due to
hyper conjugation and primary(1°) is the least stable.

Hello
a.
Less reacOve. Will form a 2°
Most reacOve. Will form a 3°
carbocaOon
carbocaOon

b. 2-methyl-2-butene 3-methyl-1-butene

Most reacOve. Will form a 3° Less reacOve. Will form a 2°

carbocaOon carbocaOon
V. Acid Catalyzed Hydration
Identify whether you would use dilute sulfuric acid or
concentrated sulfuric acid to achieve each of the following
transformations. In each case explain your choice.

OH
Hello
a.

HO

b.
V. Acid Catalyzed Hydration
Answers: Dilute sulfuric acid will result in an addition reaction. Water
will be added across the double bond (on the left side of the equation
according to Le Chatalier’s principle). If you use concentrated sulfuric
acid, the OH on the double bond will be protonated most of the time so
the rate of the elimination reaction will be greater. You will form a
double bond. Hello
OH

a. H2O + Dilue H2SO4

HO
concentrated H2SO4
b.
V. Acid Catalyzed Hydration
Draw a mechanism for each of the following transformations:

a. H 2O
[H+]

Hello

dilute
b. H2SO4

H3O+
c.
V. Acid Catalyzed Hydration
Answers: H
H
H H O
O O H H OH
O
H
a. H H

Hello
H
H H
H O
O O H
H H O H OH
b. H

H H H

O H O
O
H H H H OH
H O

c.
 V. Acid Catalyzed Hydration
If an alkene is protonated with an acid, and an alcohol is used as a
solvent instead of water, an ether(C-O-C bond) is formed as the
major product. Write a mechanism for each of the following
reactions.

Hello
EtOH
a. H2SO4

H2SO4
b. OH
V. Acid Catalyzed Hydration
Answers: The mechanism is exactly the same as when water is
added across a double bond. Instead, the alcohol will be your
nucleophile
O
H
O H
H O
O O
a. EtOH Hello H H

H2SO4

H
H H
O O
H
H
H
O
H2SO4 OH
HO
b. OH

I love example b. because it is a great way to make rings.

Five and six-membered rings form especially fast since the
O
nucleophile is tethered (or ahached) to the electrophile.
Even if water was your solvent, the ring may sill form
faster then ahack by water.
VI. Oxymercuration-Demercuration

• Markovnikov hydration (H2O, H2SO4) has limited application…

rearrangements often occur, giving mixture of products
• Especially due to carbocation rearrangements!
• Oxymercuration-demercuration is an alternative
Hello
– Markovnikov addition of H and OH
– No rearrangements occur!
VI. Oxymercuration-Demercuration

• The mercuric cation is the (Lewis) acid in this reaction, instead of H+

Hello
VI. Oxymercuration-Demercuration

• When the 𝛑 bond attacks the mercuric cation, a stabilized cation is

formed, and so it will not rearrange like carbocations do.

carbocations will
Hello rearrange if they can

Mercurinium ions
will not rearrange
(it is stabilized by the
Hg)
VI. Oxymercuration-Demercuration

• The mercurinium ion reacts with nucleophiles, and it can easily be

attacked by a nucleophile

Hello

• NaBH4 is generally used to replace the –HgOAc group with a –H

group via a free radical mechanism
VI. Oxymercuration-Demercuration

• The two reaction sequence provides same product as acid-catalyzed hydration,

but without rearrangement.

Mixture of products
formed due to a
Hello rearranged product

A 1,2-methyl shift would

occur if H2O,H2SO4
was used
• Practice with Conceptual Checkpoint 8.12
VI. Oxymercuration-Demercuration

Predict the product for each reaction and predict the products if
an acid-catalyzed hydration had been performed rather than an
oxymercuration-demercuration:

H3O+ 1. Hg(OAc)2, H2O

Hello 2. NaBH4

a.

H3O+ 1. Hg(OAc)2, H2O

2. NaBH4

b.

H3O+ 1. Hg(OAc)2, H2O

2. NaBH4

c.
VI. Oxymercuration-Demercuration

Answers: Oxymercuration still results in Maokovnikov addition of

alcohols to the most substituted carbon. However, the mercury will
stabilize the carbocation intermediate so no rearrangements will occur.
OH
OH OH

H3O+ 1. Hg(OAc)2, H2O

Hello 2. NaBH4

Racemic a. Racemic

OH

H3O+ 1. Hg(OAc)2, H2O

2. NaBH4
OH
Racemic
b.
OH OH
H3O+ 1. Hg(OAc)2, H2O
2. NaBH4

c.
VI. Oxymercuration-Demercuration

Predict the product for each reaction

Hello 1. Hg(OAc)2, EtOH

a. 2. NaBH4
O

1. Hg(OAc)2, EtNH2
b. 2. NaBH4
HN
VI. Oxymercuration-Demercuration

Answers:

Hello 1. Hg(OAc)2, EtOH

a. 2. NaBH4
O

1. Hg(OAc)2, EtNH2
b. 2. NaBH4
HN
VII. Hydroboration-Oxidation

• Hydroboration-Oxidation adds H and OH with anti Markovnikov

regioselectivity

Hello

• Note that this is a two-step reaction sequence

VII. Hydroboration-Oxidation

• Hydroboration-Oxidation is also stereoselective

– H and OH are added in a syn fashion

Hello

• Anti addition is NOT observed

VII. Hydroboration-Oxidation

• Geometry/hybridization of BH3 is analogous to a carbocation

Hello
VII. Hydroboration-Oxidation

• The boron atom does not have an octet undergo intermolecular

resonance to help fulfill their octets

Hello

• The resonance hybrid reveals three-center, two-electron bonds

VII. Hydroboration-Oxidation

• B2H6 has to be stabilized in an ether solvent so that an appreciable

amt of BH3 is present
• The active reagent is BH3•THF

Hello
VII. Hydroboration-Oxidation

• Hydroboration follows anti Markovnikov regioselectivity

• The less substituted carbon attacks the boron, and the more
substituted carbon develops a δ+ which triggers a hydride shift

Hello

• One BH3 reacts with three equivalents of alkene

VII. Hydroboration-Oxidation

• Hydroboration follows anti Markovnikov regioselectivity

• The less substituted carbon attacks the boron, and the more
substituted carbon develops a δ+ which triggers a hydride shift

Hello

• Recall that the more substituted carbon will be better at stabilizing

a positive charge
VII. Hydroboration-Oxidation

• Hydroboration follows anti Markovnikov regioselectivity

• Sterics also influence the regioselectivity

Hello
VII. Hydroboration-Oxidation

Hello
VII. Hydroboration-Oxidation

Draw the expected product(s) for the following reaction

Hello 1. BH3 - THF

2. H2O2, NaOH
VII. Hydroboration-Oxidation

Answers:

H H
1. BH3 - THF
Hello
2. H2O2, NaOH (S) (R)
OH OH

Pair of EnanOomers

If you are having difficulty, make some models at home!

Make the starting alkene, and make each expected product
(top approach or bottom approach)
VII. Hydroboration-Oxidation

• Hydroboration is stereospecific: only syn addition occurs

Hello

If only one chiral center is formed, a pair of enantiomers is formed by

addition to either side of the alkene
VII. Hydroboration-Oxidation

• Hydroboration is stereospecific: only syn addition occurs

Hello

If two chiral centers are formed, again a pair of enantiomers is

obtained.
VII. Hydroboration-Oxidation
Draw the expected product(s) for the following reaction

Hello
VII. Hydroboration-Oxidation
Answers:
• Two chirality centers are formed. Why do we not obtain a
mixture of enantiomers? (Answer, because one of the
stereocenters is set (the one containing the methyl group).
Therefore these are NOT mirror images of each other.
Hello

In this case, a mixture

of diastereomers is obtained
VII. Hydroboration-Oxidation
Draw the expected product(s) for the following reaction

a. 1. BH3·THF
2. H2O2, NaOH
Hello

b. 1. BH3·THF
2. H2O2, NaOH

c. 1. BH3·THF
2. H2O2, NaOH
VII. Hydroboration-Oxidation
Answers: This one is straight forward since no chiral centers are
formed.

a. 1. BH3·THF
OH
2. H2O2, NaOH
Hello

OH
b. 1. BH3·THF
2. H2O2, NaOH

c. 1. BH3·THF
2. H2O2, NaOH
OH
VII. Hydroboration-Oxidation
Draw the expected product(s) for the following reaction

1. BH3·THF
d. 2. H2O2, NaOH

Hello

e. 1. BH3·THF
2. H2O2, NaOH

1. BH3·THF
f. 2. H2O2, NaOH
 VII. Hydroboration-Oxidation
Answers: This one gets tricky because chiral centers may be
formed. Remember that the H and the OH are added syn.
However, the H is not shown in the product.

d. 1. BH3·THF
2. H2O2, NaOH
Hello OH OH
Since the H and OH are added syn to one another, the methyl and alcohol end
up anO. Remember the H (which is syn to the OH) is not drawn in the diagram.
OH OH

e. 1. BH3·THF
2. H2O2, NaOH

OH
1. BH3·THF
f. 2. H2O2, NaOH
VII. Hydroboration-Oxidation
Draw the expected product(s) for the following reaction

g. 1. BH3·THF
2. H2O2, NaOH

Hello
1. BH3·THF
h. 2. H2O2, NaOH

1. BH3·THF
2. H2O2, NaOH
i.

1. BH3·THF

j. 2. H2O2, NaOH
VII. Hydroboration-Oxidation
Answers:
HO HO
g. 1. BH3·THF
2. H2O2, NaOH

Hello
1. BH3·THF HO
h. 2. H2O2, NaOH

1. BH3·THF
2. H2O2, NaOH
i. OH OH

I think this problem is interesOng

because only one product is
formed. The BH3 can NOT
1. BH3·THF
j. 2. H2O2, NaOH H H
approach from the top since the
giganOc gem-dimethyl group blocks
OH the top face of the ring. BH3 can
only approach from the bogom.
VII. Hydroboration-Oxidation
Propose a structure for compound A based off of the given
information.

Hello OH

A 1. BH3·THF
2. H2O2, NaOH

OH
VII. Hydroboration-Oxidation

Answer: Think backwards. What starting alkene will give you the
following product distribution?

Hello
OH
1. BH3·THF
2. H2O2, NaOH

OH
VIII. Catalytic Hydrogenation

• Hydrogenation - the addition of H2 across a C=C double bond

• Requires a metal catalyst
• Alkene is converted to the corresponding alkane

Hello
VIII. Catalytic Hydrogenation

• Hydrogenation - the addition of H2 across a C=C double bond

• Stereospecific – only syn addition is observed with hydrogenation

Hello

Two chirality centers are formed

only the stereoisomers resulting
from syn addition are obtained
VIII. Catalytic Hydrogenation

• Without the metal catalyst, the addition of H2 is too slow due to a

very high activation energy (Ea)

Hello
VIII. Catalytic Hydrogenation

• The metal surface binds the H2, and the alkene, which explains
why H atoms are added syn across the π bond

Hello
VIII. Catalytic Hydrogenation

• Syn addition of H2 to a symmetrical alkene will not produce a pair

of enantiomers.
• A meso compound will be produced instead

Hello
VIII. Catalytic Hydrogenation

• Heterogenous catalyst: Does not dissolve in reaction medium, like

Pt or Pd metal.
• Homogenous catalyst: Does dissolve in the reaction medium,
accomplished by using a ligand with the metal to make it soluble
Hello

Wilkinson’s catalyst
(3-PPh3 ligands, 1-Cl ligand)
VIII. Catalytic Hydrogenation

• Recall that the creation of one or two chiral centers results in a

mixture of enantiomers (unless a meso compound is produced)

Hello
VIII. Catalytic Hydrogenation
• If a chiral catalyst is used, it is possible to synthesize only one
enantiomer as the major product
• This can be accomplished by replaced the phosphine ligands on
the Wilkinson catalyst with chiral phosphine ligands

Hello

• Oftentimes, there is no easy way to tell what enantiomer will be

synthesized before hand. You just have to pick a chiral catalyst,
and give it a shot. If you made the wrong enantiomer, then use
the enantiomer of your starting catalyst.
VIII. Catalytic Hydrogenation

• If a chiral catalyst is used, it is possible to synthesize only one

enantiomer as the major product
• William S. Knowles developed a synthesis of L-Dopa using a
asymmetric hydrogenation as the key step
Hello

• He later won the Nobel Prize in 2001

• L-Dopa increases the levels of dopamine in the brains of patients with
Parkinson’s disease. The (R) enantiomer is believed to be toxic.
VIII. Catalytic Hydrogenation

• If a chiral catalyst is used, it is possible to synthesize only one

enantiomer as the major product
• Ryoji Noyori showed that the chiral ligand BINAP also affords one
enantiomer with high selectivity
Hello

• For his work, Noyori also won the Nobel Prize (with Knowles) in 2001.
• BINAP is used ALL THE TIME (although, every time I needed to use
BINAP for a reaction, I got horrible enantioselectivity)
VIII. Catalytic Hydrogenation

Predict the product(s) for each of the following reactions

H2
a. Pt
Hello

H2
b. Pt
VIII. Catalytic Hydrogenation
Answers: Remember, with these hydrogenation reactions, the H’s
are added through syn addition (H’s added to the same side).
Also, be on the lookout for stereocenters.

a. H2 Hello
H H
=
Pt
H H

Two chiral centers are formed

b. H
H
H
H
H2
=
Pt

Only one chiral center is formed

VIII. Catalytic Hydrogenation
Predict the product(s) for each of the following reactions

H2

a. Ni

Hello
b. H2
Pd

c. H2
Ni

d. H2
Pt

e.
H2
Pd
VIII. Catalytic Hydrogenation
Answers: Remember, the H’s are added to the same side of the
double bond and always look out for new chiral centers.

No chiral centers formed

a. H2
Ni

Hello
b. H2 No chiral centers formed
Pd

c. H2
One chiral center formed.
A mixture of enanOomers
Ni is obtained.

d. H2
Pt No chiral centers formed

This compound is meso so

e. H2
there is only one product.
Pd
Make a model if you need to
prove it to yourself
IX. Halogenation and Halohydrin Formation.

• Halogenation – addition of two halogen atoms across a C=C double

bond

Hello

• Halogenation is a key step in the production of PVC (white PVC pipes)

Radical
Mechanism
IX. Halogenation and Halohydrin Formation.
Without looking ahead, what products are possible, and what is
a possible mechanism for this reaction.

Hello
IX. Halogenation and Halohydrin Formation.

• Halogenation only practical with Cl2 and Br2

• halogenation with I2 is poor; halogenation with F2 is too violent

• Regioselectivity – halogenation occurs with anti addition

Hello
IX. Halogenation and Halohydrin Formation.

• Br2 is nonpolar, but polarizable. Approach of a nucleophile will

induce a dipole
• Think of Br2 as a bromine atom bonded to a good leaving group

Hello

The alkene acts as the nucleophile

If this was the mechanism(but it is not) we would expect to

see syn and anti addition.
IX. Halogenation and Halohydrin Formation.

• Only anti addition is observed, so the mechanism is not consistent

with a true carbocation intermediate
• Syn addition doesn’t occur

Hello
IX. Halogenation and Halohydrin Formation.

• The formation of a bromomium ion intermediate is consistent

with anti addition
• This intermediate is similar to the mercurinium ion

Hello
IX. Halogenation and Halohydrin Formation.

• The formation of a bromomium ion intermediate is consistent

with anti addition
• Br− attacks backside (anti) to the bromonium ion

Hello
IX. Halogenation and Halohydrin Formation.
Without looking ahead, what products are possible with this
reaction? Draw a mechanism for practice

Br2
Hello

Br2
IX. Halogenation and Halohydrin Formation.

• Halogenation is stereospecific, the stereochemistry of the starting

alkene determines the stereochemistry of the product(s)

Hello
VIII. Catalytic Hydrogenation
Without looking ahead, what products are possible, and what is
a possible mechanism for this reaction.
Use Logic! Think back to what you know already and then
apply that knowledge to this reaction!
Hello

Br2
H 2O
IX. Halogenation and Halohydrin Formation.

• Halohydrins – formed when halogenation is conducted in water

• Water acts as the nucleophile that attacks the bromonium ion

Hello

• There are many more H2O molecules compared to Br− ions, so H2O
outcompetes Br− for the bromonium ion
IX. Halogenation and Halohydrin Formation.

• After water attacks, it is deprotonated to yield the neutral

bromohydrin product

Hello

Here, the product is called

a chlorohydrin
VIII. Catalytic Hydrogenation
Without looking ahead, what products are possible, and what is
a possible mechanism for this reaction.

Br2
H 2O
Hello
IX. Halogenation and Halohydrin Formation.

• Halohydrin Formation is regioselective

– The halide adds to the less substituted carbon
– The OH adds to the more substituted carbon

Hello
IX. Halogenation and Halohydrin Formation.

• Regioselectivity results from H2O attacking the more substituted

carbon (faster than it attacks the less substituted one)

Hello
IX. Halogenation and Halohydrin Formation.

• Regioselectivity results from H2O attacking the more substituted

carbon (faster than it attacks the less substituted one)

Hello

Transition state (like an average of your

three resonance forms)
• The more substituted carbon has more cationic character.
• Never forget your possible resonance structures when dealing
with cationic character!
Br Br
Br

Minor Resonance Form Major Resonance Forms

IX. Halogenation and Halohydrin Formation.
Predict the major product(s) for each of the following reactions:

a. Br2

Hello
b. Br2
H 2O

c. Br2

d. Br2
H 2O
IX. Halogenation and Halohydrin Formation.
Answers:
Br
Br
Br2
a. Br
Br

Hello
Br Br
Remember, the second
b.
Br2
H 2O addiOon always occurs on the
HO OH more stabilized carbocaOon.

Br Br

c. Br2

Br Br

HO OH
Remember, the second
d. Br2
H 2O
Br Br addiOon always occurs on the
more stabilized carbocaOon.
IX. Halogenation and Halohydrin Formation.
Predict the major product(s) for each of the following reactions:

Br2
e.

Hello
f.
Br2
EtOH

g. Br2
H 2O

Br2
h.
IX. Halogenation and Halohydrin Formation.
Answers:
Br Br

e. Br2 Br Br

Hello
Br Br
Remember, the second
f. Br2
addiOon always occurs on the
EtOH
O O more stabilized carbocaOon.

OH OH Remember, the second

addiOon always occurs on the
g. Br2 Br Br
more stabilized carbocaOon.
H 2O

Br Br

h. Br2

Br Br
IX. Halogenation and Halohydrin Formation.
Predict the major product(s) for each of the following reactions:

i. Br2
Hello
H 2O

Br2
j. EtNH2
IX. Halogenation and Halohydrin Formation.
Answers:

Br Br
i. Br2
Hello
H 2O
OH OH

HN NH
j.
Br2
EtNH2

Br Br
IX. Halogenation and Halohydrin Formation.
When running this reaction four different products were
obtained. Rationalize this observation.
Br Br

Br2

Hello Br Br

an. addiOon products (80% yield)

Br Br

Br Br

syn addiOon products (20% yield)

IX. Halogenation and Halohydrin Formation.
Answer: The anti addition occurs as expected however, the
brominum ion can actually open up since the resulting
carbocation is stabilized by the phenol ring.

Hello

Br

Resonance Stabilized!
X. Anti Dihydroxylation

• Dihydroxylation – addition of OH and OH across the π bond

Hello

• Anti dihydroxylation of an alkene is a two-reaction process

X. Anti Dihydroxylation

1. Conversion of alkene to an epoxide:

Hello

• A peroxyacid is used as the reagent

X. Anti Dihydroxylation

1. Conversion of alkene to an epoxide:

2. The epoxide is reacted with H2O and acid catalyst to form the anti
diol.

Hello
X. Anti Dihydroxylation

• Note the similarities between these three key intermediates

Hello

• Ring strain and a +1 formal charge makes these structures good

electrophiles
• They also each yield anti products, because the nucleophile must
attack from the side opposite the leaving group
X. Anti Dihydroxylation
Predict the major product(s) for each of the following reactions:

a. 1. CH3CO3H
Hello
2. H3O+

1. CH3CO3H
b. 2. H3O+
X. Anti Dihydroxylation
Answers: The mechanism for this reaction is virtually identical to
the last reaction (halohydrin formation utilizing a bromonium ion).
The second attack occurs anti and on the most substituted carbon.
Also don't forget, there are many different ways to draw the
structure of the answer and still be correct.
Hello
OH OH
a. 1. CH3CO3H
2. H3O+ HO
OH

OH OH

b. 1. CH3CO3H
2. H3O+
OH OH
X. Anti Dihydroxylation
Predict the major product(s) for each of the following reactions:

a. 1. CH3CO3H
2. H3O+

Hello
1. CH3CO3H
b. 2. H3O+

1. CH3CO3H

c. 2. H2SO4, EtOH

1. CH3CO3H

d. 2. H3O+
X. Anti Dihydroxylation
Answers: Remember, the second addition always occurs at the
more substituted carbon (more stable carbocation)
HO OH
OH

a.
1. CH3CO3H
2. H3O+ OH

Hello
HO OH HO OH
1. CH3CO3H
b. 2. H3O+

O O

c.
1. CH3CO3H
2. H2SO4, EtOH

OH OH

OH OH

d.
1. CH3CO3H
2. H3O+
OH OH
X. Anti Dihydroxylation
Predict the major product(s) for each of the following reactions:

e. 1. CH3CO3H
2. H3O+

Hello
1. CH3CO3H
f. 2. H3O+

g.
1. CH3CO3H
2. H3O+

h. O
OH

Enantiomerically H2SO4
Pure
X. Anti Dihydroxylation
Answers: Remember, the second addition always occurs at the
more substituted carbon (more stable carbocation)
OH

e. 1. CH3CO3H
2. H3O+ OH

OH
HO OH
1. CH3CO3H
=
f. Hello
2. H3O+
OH

OH
1. CH3CO3H OH

g. 2. H3O+
OH OH

h. O
OH
O

Enantiomerically H2SO4
Pure OH
I am not sure if I believe this answer, and if it is true, the percent yield may be quite low. In a perfect
world yes, the nucleophile will add to the most subsOtuted carbon. However, steric hinderance may play
a role here and I don't know how easy it will be for the phenol (which is very large) to approach the back
side of the epoxide with that methyl group in the way. It may have a lot of SN1 character.
XI. Syn Dihydroxylation

• syn dihydroxylation – adds OH and OH across the p bond, in a

concerted, syn fashion.

Hello
XI. Syn Dihydroxylation

• OsO4 is expensive, and toxic.

• NMO or an alkyl peroxide is used as an co-oxidant, so only a
catalytic amount of OsO4 is necessary.

Hello
XI. Syn Dihydroxylation

• Syn dihydroxylation can also be achieved with KMnO4 but only

under mild conditions (cold temperatures)

Hello

• The synthetic utility of MnO4− is limited: it reacts with many other

functional groups as well
XI. Syn Dihydroxylation
Predict the major product(s) for each of the following reactions:

OsO4 (catalytic)
a. NMO

Hello
1. OsO4
b. 2. NaHSO3 / H2O

KMnO4, NaOH

c. Cold
XI. Syn Dihydroxylation
Answers: Make sure that the OH’s always end up syn to one
another. Also, keep an eye out for chiral centers and meso
compounds!
OH OH
OsO4 (catalytic)
a. NMO
Hello
OH OH

OH OH
1. OsO4
b. 2. NaHSO3 / H2O OH OH

OH
KMnO4, NaOH
c. Cold
OH
Meso compound.
This is the only product.
XI. Syn Dihydroxylation
Predict the major product(s) for each of the following reactions:

KMnO4, NaOH

d. Cold

Hello
OsO4 (catalytic)

e. OOH

OsO4 (catalytic)

f. NMO
XI. Syn Dihydroxylation
Answers: Make sure that the OH’s always end up syn to one
another. Also, keep an eye out for chiral centers and meso
compounds!

OH
This is the only product. There are
d. Hello
KMnO4, NaOH
Cold no chiral centers in this molecule.
OH

OH OH
OsO4 (catalytic)

e.
OH OH
OOH

OH OH
f. OsO4 (catalytic)
NMO
OH OH
XII. Oxidative Cleavage
• C=C double bonds are also reactive toward oxidative cleavage
• Ozonolysis is one such process (Very Important Reaction)

Hello

• Ozone exists as a resonance hybrid of two contributors

I picture myself cutting the C=C with scissors pulling it apart and
connecting each double bond to an oxygen R-C=O O=C-R
XII. Oxidative Cleavage

Hello

• Common reducing agents include dimethyl sulfide and Zn/H2O.

XII. Oxidative Cleavage
Predict the major product(s) for each of the following reactions:

a. 1. O3
2. DMS

Hello

b. 1. O3
2. DMS

c. 1. O3
2. DMS
XII. Oxidative Cleavage
Answers: Every time you see a double bond, break it and write
two carbonyls (C=O’s) in its place. It may be helpful to count (or
write numbers) next to each carbon so you can make sure you
draw the correct product.
O O
Hello O
a. 1. O3
2. DMS
H
O

O O O O
b. 1. O3
2. DMS

O O
c. 1. O3
2. DMS
H H
XII. Oxidative Cleavage
Predict the major product(s) for each of the following reactions:

1. O3
d. 2. DMS

Hello

1. O3
e. 2. DMS

1. O3

f. 2. DMS
 XII. Oxidative Cleavage
Answers: Every time you see a double bond, break it and write
two carbonyls (C=O’s) in its place. It may be helpful to count (or
write numbers) next to each carbon so you can make sure you
draw the correct product.
1. O3 H H

d. Hello
2. DMS
O O

O O
1. O3
e. 2. DMS H H

This one is tricky in that we tend to forget to indicate the

stereochemistry. Use the starOng material as your guide.
O O
1. O3

f. 2. DMS
XII. Oxidative Cleavage

Predict a bicyclic reactant used to form the product below

H
Hello 1) O3
S O H
2)

H O O
XII. Oxidative Cleavage
Identify the structure of the starting material.

O O
a. C8H14
1. O3
2. DMS

Hello O
1. O3
b. C10H16
2. DMS

O O
1. O3
C10H16
c. 2. DMS
XII. Oxidative Cleavage
Answers: Basically you want to remove all of the =O’s and connect
them together to see what your original alkene will be. Use the
starting molecular formula to guide you in this process.

O O
a. Hello
1. O3
2. DMS

O
1. O3
b. 2. DMS

O O
1. O3
c. 2. DMS
XII. Oxidative Cleavage

Answer: Try to connect up the carbonyls and see what starting

materials are possible. In this case there is only one product possible
since we can not have a double bond in a 3 or 4 membered ring due
to ring strain (orbitals can not overlap properly)
Hello
O

H
1) O3
S O H
2)

H O O
XIII. Predicting Products of Addition Reactions

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)
Hello
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
XIII. Predicting Products of Addition Reactions

• To set up a synthesis, assess the reactants and products to see

what changes need to be made

Addition reaction

Hello

Substitution reaction

Elimination reaction
XIII. Predicting Products of Addition Reactions

• 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

Hello

Here, we need to do an
addition reaction, and add H
and OH, Markovnikov
XIII. Predicting Products of Addition Reactions

• 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

Hello
H2O, H2SO4
XIII. Predicting Products of Addition Reactions
Predict the product(s) of each of the following reactions

1. BH3·THF
a. 2. H2O2, NaOH

Hello
H2
b. Pt

1. CH3CO3H

c. 2. H3O+
 XIII. Predicting Products of Addition Reactions
Answers: This requires lots and lots of practice. Keep going back
to your notebook of reactions and all of the review questions in
this chapter.

a. 1. BH3·THF OH
2. H2O2, NaOH
Hello

b. H2
Pt

OH OH

c.
1. CH3CO3H
2. H3O+
HO OH
XIII. Predicting Products of Addition Reactions
Predict the product(s) of each of the following reactions

d.
1. OsO4
2. NaHSO3 / H2O

Hello

e. H3O+

HBr

f.
 XIII. Predicting Products of Addition Reactions
Answers: This requires lots and lots of practice. Keep going back
to your notebook of reactions and all of the review questions in
this chapter.
OH

d.
1. OsO4
2. NaHSO3 / H2O OH
Hello
OH OH

OH OH
e. H3O+

Br

f. HBr
XIII. Predicting Products of Addition Reactions
Predict the product(s) of each of the following reactions

1. RCO3H
g. 2. H3O+

Hello
1. BH3·THF
h. 2. H2O2, NaOH

OsO4 (catalytic)
i. NMO
 XIII. Predicting Products of Addition Reactions
Answers: This requires lots and lots of practice. Keep going back
to your notebook of reactions and all of the review questions in
this chapter.
OH OH

g. 1. RCO3H
Hello
2. H O +
3

OH OH

OH OH

h. 1. BH3·THF
2. H2O2, NaOH

OH HO

i. OsO4 (catalytic)
NMO
HO OH
XIII. Predicting Products of Addition Reactions
Predict the products of the following reaction and describe their
relationship to one another.

Hello
KMnO4, NaOH
Cold
XIII. Predicting Products of Addition Reactions
Answer: Since the stereochemistry of the methyl group is set, the
products are diastereomers. Notice how that methyl group
prevents the products from being mirror images of one another

Hello OH OH
KMnO4, NaOH
Cold
OH OH
XIV. Multistep Synthesis

• Changing the position of a Leaving Group:

The following transformation cannot be done with a single reaction

Hello

It can be accomplished in a two-reaction sequence:

XIV. Multistep Synthesis

• Changing the position of a Leaving Group:

To do the elimination reaction, the base needs to be carefully chosen:

This is the alkene we need,

Hello so we use non-bulky base.
(Thermodynamic Product)

Undesired Kinetic Product

XIV. Multistep Synthesis

• Changing the position of a Leaving Group:

Then we need to decide the reagents needed to add H and Br:

Hello

Markovnikov addition of
So, overall: H and Br
XIV. Multistep Synthesis

• Consider the following transformation:

Hello
• This is not a simple substitution, addition or elimination, so two
processes must be combined
XIV. Multistep Synthesis

• The elimination must be done to give the Hofmann alkene, via an

E2 elimination

Hello
Kinetic Product

• The alcohol must be changed to a good leaving group so we can

use a bulky base to afford the Hofmann product:
XIV. Multistep Synthesis

• The addition reaction must give anti Markovnikov addition of H

and OH
• So, overall:

• Hello
XIV. Multistep Synthesis

• Changing the position of a π bond:

Hello
• Again, two processes must be combined

anti Markovnikov elimination to give

addition of H and Br the Hofmann product
XIV. Multistep Synthesis

• Changing the position of a π bond:

• Now recall the reagents needed for each reaction:

Hello

anti Markovnikov elimination to give

addition of H and Br the Hofmann product
HBr , ROOR t-BuOK
(anti Markovnikov) (bulky base)
XIV. Multistep Synthesis

• Ten reactions of alkenes covered in this chapter:

Hello
 XIV. Multistep Synthesis

You might want to add this to your reaction notebook before the section on alkenes (kinda like a table of contents)
XIV. Multistep Synthesis
Identify the reagents that you would use to accomplish each of
the following transformations:
OH

a.

Hello
Br
b.

Br
c.

d.
XIV. Multistep Synthesis
Answers: Practice, practice, practice!!
OH OH

1. BH3·THF
a.
2. H2O2, NaOH

Hello
Br
t-BuOK
b.

HBr Br
c.
ROOR

H2
d.
Pt
XIV. Multistep Synthesis
Identify the reagents that you would use to accomplish each of
the following transformations:
Cl

e.

Hello

f. OH

Br
g.

Br

h.
XIV. Multistep Synthesis
Answers: Practice, practice, practice!!
Cl
HCl
e.

Hello
1. BH3·THF
f. OH OH
2. H2O2, NaOH

Br
NaOEt
g.

Br
HBr
h.
XIV. Multistep Synthesis
Identify the reagents that you would use to accomplish each of
the following transformations:
Cl

a.
Cl

OH
Hello
HO
b.

Br
HO
c.

OH

d.

OH OH
XIV. Multistep Synthesis
Answers: Practice, practice, practice!!
Cl
NaOEt HCl
a.
Cl

OH Hello
1. TsCl, py. 1. BH3·THF
HO
b.
2. t-BuOK 2. H2O2, NaOH

Br HO
t-BuOK 1. BH3·THF
c.
2. H2O2, NaOH

OH
1. TsCl, py. 1. BH3·THF
d.
2. NaOEt 2. H2O2, NaOH
OH OH

conc. H2SO4
heat
XIV. Multistep Synthesis
Identify the reagents that you would use to accomplish each of
the following transformations:

a.

Hello

b.

c.

d.
XIV. Multistep Synthesis
Answers
Br

HBr NaOMe
a.

HBr
Hello NaOMe
b. Br
t-BuOK HBr

Br
HBr NaOEt 1. HBr, ROOR
c.
2. t-BuOK

Br
1. HBr HBr, ROOR t-BuOK
d.
2. NaOMe