Chapter 8

Addition Reactions of
Alkenes

1
 8.1 Introduction to Addition Reactions
• Addition is the opposite of elimination

• C=C p bond is converted to two new

sigma bonds

• The p bond is an electron-pair donor

2
 8.2 Alkenes in Nature and Industry
• Naturally occurring, acyclic alkenes: • Cyclic and polycyclic alkenes:

• 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.

3
 8.3 Nomenclature of Alkene
• Alkenes are named by following the same IUPAC naming procedure to
name alkanes, with minor modifications
1. Identify the parent chain, which includes the C=C double bond.
2. Identify and Name the substituents.
3. Assign a locant (and prefix if necessary) to each substituent. Give the C=C
double bond the lowest number possible.
4. List the numbered substituents before the parent name in alphabetical order.
Ignore prefixes (except iso) when ordering alphabetically.
5. The C=C double bond locant is placed either just before the parent name or
just before the -ene suffix.
1. Identify the parent chain, which should include the C=C double bond.
• The name of the parent chain should end in -ene rather than –ane.

• The parent chain should include the C=C double bond.

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2. Identify and Name the substituents.
3. Assign a locant (and prefix if necessary) to each substituent. Give the C=C
double bond the lowest number possible.

4. List the numbered substituents before the parent name in alphabetical order.
Ignore prefixes (except iso) when ordering alphabetically.
5. The C=C double bond locant is placed either just before the parent name or just
before the -ene suffix.

Note: This alkene has the E configuration, which must be indicated in the name, in
parentheses: (E)-5,5,6-trimethylhept-2-ene.
• Recall how to assign E or Z to
alkene stereoisomers. (Ch5.11)

5
Try P. 8.1–8.4
 8.4 Addition vs. Elimination
• Addition and elimination are equilibrating reactions:
– Which side is favored depends on temperature.

– The higher the temperature, the more important entropy becomes:

Higher temp means

a bigger entropy term

• Addition reactions are favored by enthalpy.

• Sigma bonds are stronger (more stable) than p bonds.
TWO reactants ONE product DH = Bonds broken – bonds formed
DH = 166 kcal/mol – 185 kcal/mol
DH = –19 kcal/mol
• Addition reactions are NOT favored
by entropy.
• Two molecules combine to form one
product; entropy decreases. 6
• 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.

8.5 Hydrohalogenation
Regioselectivity:

• Hydrohalogenation: addition of H-X

(HCl, HBr, or HI)to an alkene.

• If the alkene is not symmetrical, then two

regioisomers are possible, depending on
which carbon gets the “H” and the “X” . 7
Markovnikov addition = “Markovnikov’s rule”:
• In 1869, Markovnikov observed the H atoms tend to add to the carbon already
bearing more H atoms (= H atom is added to less substituted carbon)
• The halogen is generally installed at the more substituted carbon

• When peroxides are used with HBr,

the opposite regioselectivity is
observed. (Anti-Markovnikov)
• The reaction mechanism must be
different, when peroxides are
present.
8
Ch. 10.10
P. 8.5: Draw the expected major product for each of the following reactions.

P. 8.6: Identify the reagents that you would use to achieve each of the following transformations:

9
Mechanism for Hydrohalogenation: 2 step process

• The step with the highest Ea is the

rate determining step, which is the
formation of the carbocation
intermediate (the first step).
• Markovnikov product is formed
because of carbocation stability:

Markovnikov pathway: Anti-Markovnikov pathway:

3˚ carbocation 10
2˚ carbocation
intermediate
• The Markovnikov product is formed through a lower energy (i.e. faster) transition
state.

P. 8.7: Draw a mechanism for each of the following transformations:

11
Stereochemistry for Hydrohalogenation:
• Hydrohalogenation may result in the formation of a stereogenic center.
• There are actually TWO Markovnikov products formed in this reaction.

Two enantiomers formed

in equal amounts

• The carbocation intermediate can be

attacked from either side of the empty
p-orbital, with equal probability.

P. 8.9: Predict the products for each of the following reactions. Note: in some cases, the reaction
produces a new chiral center, while in other cases, no new chiral center is formed:

12
Carbocation Rearrangements in Hydrohalogenation:
• Recall carbocations can rearrange (hydride or methide shift) if they can become
more stable.
1,2-hydride shift

• When this alkene undergoes

hydrohalogenation, the 2˚
carbocation could rearrange to a
more stable, 3˚ carbocation.

P. 8.10: Draw a mechanism for each of the following transformations

13
 8.6 Acid-catalyzed Hydration
Hydration = The components of water (H and OH) are added across the p bond
• Acid-catalyzed hydration follows Markovnikov regioselectivity.
• Sulfuric acid is typically the acid catalyst used.

• The OH is added to the more substituted carbon of

the alkene.
• The more substituted the carbon atom is, the faster
the reaction.
• The mechanism for acid-catalyzed hydration is
essentially the same as hydrohalogenation:

14
P. 8.12: In each of the following cases, identify the alkene that is expected to be more reactive
toward acid-catalyzed hydration.

Controlling the Position of Equilibrium: thermodynamics

• The reactants and products of hydration are in equilibrium
• We exploit La Chatelier’s principle to control the equilibrium
• 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 use acid, and
not add water to the reaction.

15
Stereochemistry of Acid-catalyzed Hydration:
• The stereochemistry of hydration is analogous
to hydration, for the same reason(s).
• If a new chirality center is formed, a mixture of
R and S is obtained.

P. 8.14 & 8.15: Draw a mechanism for each of the following transformations.

16
 8.7 Oxymercuration-Demercuration
• Markovnikov hydration (H2O, H2SO4) has limited application… rearrangements
often occur, giving mixture of products.
• Oxymercuration-demercuration is an alternative.
– Markovnikov addition of H and OH.
– No rearrangements occur.

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

• When the p bond attacks the mercuric cation, a stabilized cation is formed, and so it
will not rearrange like carbocations do. Mercurinium ions
carbocations will will not rearrange
rearrange if they can

17
• The mercurinium ion reacts with nucleophiles, and it can easily be attacked by a
nucleophile.
• NaBH4 is generally used to replace the –HgOAc group with a –H group via a free
radical mechanism.

• A 1,2-methide shift would occur if H2O,H2SO4 was used

• Mixture of products formed due to a rearranged product
P. 8.16 & 8.17: Predict the product for each reaction and predict the products if an acid-catalyzed
hydration had been performed rather than an oxymercuration-demercuration.

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 8.8 Hydroboration-Oxidation
• Hydroboration-Oxidation adds H and OH with anti-Markovnikov regioselectivity.
• Note that this is a two-reaction sequence.

• Hydroboration-Oxidation is also
stereoselective: H and OH are
added in a syn fashion.

• Anti addition is NOT observed.

• Geometry/hybridization of BH3 is analogous to a carbocation:

• The boron atom does not have an octet. 19

• The resonance hybrid reveals three-center, two-electron bonds.
• B2H6 has to be stabilized in an ether solvent
so that an appreciable amt of BH3 is present.
• The active reagent is BH3•THF

Mechanism of Hydroboration-Oxidation: anti-Markovnikov regioselectivity

• Hydroboration follows anti Markovnikov regioselectivity: The less substituted
carbon attacks the boron, and the more substituted carbon develops a d+ which
triggers a hydride shift.

Electronic
consideration

Steric
consideration

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P. 8.18: Consider the expected regioselectivity and then draw the product.
P. 8.19: Draw the structure of compound A.

21
Stereospecificity of Hydroboration-Oxidation:
• Hydroboration is stereospecific: only syn addition occurs.

P. 8.20: Consider the expected regioselectivity and then draw the product.

22
 8.9 Catalytic Hydrogenation
• Hydrogenation - the addition of H2 across a C=C double bond.
• Requires a transition metal catalyst (Pt, Pd, Ni, Ru…).
• Alkene is converted to the corresponding alkane.

• Stereospecificity : only syn addition is observed with hydrogenation.

• Two stereocenters are formed.
• Stereoisomers resulting from syn addition are obtained.

• Without the metal catalyst, the addition of H2 is too slow due to a very high activation
energy (Ea).
• The metal surface binds the H2 and the
alkene, which explains why H atoms
are added syn across the p bond.

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P. 8.22: Predict the product(s) for each of the following reactions.

• Heterogenous catalyst – does not dissolve in reaction medium, like Pt or Pd metal.

• Homogenous catalyst – soluble in the reaction medium, accomplished by using a
ligand with the metal.

Wilkinson’s catalyst

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Asymmetric 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.

Noyori, 2001
Nobel Prize

8.10 Halogenation and Halohydrin Formation

Halogenation – addition of two halogen atoms across a C=C double bond.
• Halogenation is a key step in the production of PVC.

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• Halogenation only practical with Cl2 and Br2
• Halogenation with I2 is poor; halogenation with F2 is too violent
• Regioselectivity – halogenation occurs with anti-addition

• 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

• The formation of a bromomium ion

intermediate is consistent with anti addition.

• Only anti addition is observed, so the

mechanism is not consistent with a true
carbocation intermediate. 26
• Syn addition doesn’t occur.
• Halogenation is stereospecific, the
stereochemistry of the starting alkene
determines the stereochemistry of
the product(s).

P. 8.24: Predict the product(s) for each of the following reactions.

Halohydrins : formed when halogenation is conducted in water.

• Water acts as the nucleophile that attacks the bromonium ion.
• There are many more H2O
molecules compared to Br -
ions, so H2O outcompetes
Br - for the bromonium ion.
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• Halohydrin Formation is regioselective
– The halide adds to the less substituted carbon.
– The OH adds to the more substituted carbon.

• Regioselectivity results from H2O attacking the more substituted carbon (faster than it
attacks the less substituted one).

The more substituted

carbon has more
cationic character.
P. 8.25 & 8.26: Predict the major product(s) that are expected when each of the following alkenes is
treated with Br2/H2O.

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 8.11 Anti-Dihydroxylation
• Dihydroxylation – addition of
OH and OH across the p bond.

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

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• Note the similarities between these three key intermediates

• Ring strain and a +1 formal charge makes these structures good electrophiles
• They also yield anti products, because the nucleophile must attack from the side
opposite the leaving group.
P. 8.28 & 8.29: Predict the products that are expected when each of the following alkenes is treated
with a peroxy acid (RCO3H) followed by aqueous acid.

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 8.12 Syn Dihydroxylation
• Syn-dihydroxylation – adds OH and OH across the p bond, in a concerted, syn-
fashion.

• OsO4 is expensive, and toxic.

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

• Syn dihydroxylation can also be achieved with KMnO4 but only under mild conditions
(cold temperatures)
• The synthetic utility of MnO4- is limited: it reacts with many other functional groups as
well.

31
P. 8.31: Predict the product(s) for each of the following reactions. In each case, make sure to
consider the number of chiral centers being formed.

8.13 Oxidative Cleavage

• C=C double bonds are also reactive toward oxidative cleavage.
• Ozonolysis is one such process.
• Ozone exists as a resonance hybrid of two contributors.

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 Common reducing agents include
dimethyl sulfide and Zn/H2O.

SBP. 8.8: Predict the products of the following reaction.

P. 8.32 & 8.33: Predict the products / starting materials of the following reaction.

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 8.14 Predicting Products of Addition Reactions
1. What are the identities of the groups being added across the double bond?
2. What is the expected regioselectivity (Markovnikov or anti-Markovnikov addition)?
3. What is the expected 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.
P. 8.35: Predict the products of each of the following reactions.

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 8.15 Synthesis Strategies
One-Step Syntheses:

Addition reaction Substitution reaction Elimination reaction

SBP. 8.10: Identify the reagents that you would use to accomplish the following transformation:

OH
• To set up a synthesis, assess the reactants and
products to see what changes need to be made.

Here, we need to do an addition rxn, and add H and OH, Markovnikov

OH
H2O, H2SO4 • Give reagents and conditions: H2O, H2SO4

Try 8.39, 8.40

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Multi-Step Syntheses: Changing the position of a Leaving Group

• The following transformation cannot be done with a single reaction.

• It can be accomplished in two steps:

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

This is the alkene we need,
so we use non-bulky base

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

NaOMe HBr

Markovnikov addition 36
of H and Br
• Consider the following transformation:

• This is not a simple substitution, addition or elimination, so two processes must

be combined.

• The elimination must be done to give the Hofmann alkene, via an E2 elimination
• The alcohol must be changed to a good leaving group so we can use a bulky
base to afford the Hofmann product:

• The addition reaction must give anti-Markovnikov addition of H and OH.

• So, overall:

37
Multi-Step Syntheses: Changing the position of a p bond

• Again, two processes must be combined.

anti Markovnikov elimination to give the

addition of H and Br Hofmann product

HBr , ROOR t-BuOK

(anti-Markovnikov) (bulky base)

Try Problem 8.42 – 46

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Review of Addition Reactions

39