Module H Occurrence of Alkenes

Alkenes Structure and Reactivity:  Alkenes are hydrocarbons with a C=C double bond
functional group
Addition via Carbocations  Also called “olefins”

Bruice’s Organic Chemistry: Chapters 5-6

 Includes many naturally occurring materials
Learning Outcomes:  Flavors, vitamins, monomers for polymerization
1. What is the characteristic structure and reactivity of alkenes?
2. What is the mechanism and outcome of the addition of HX to alkenes?
3. What is the stability, reactivity and implications of carbocation intermediates?
4. What is the mechanism and outcome of the addition of water and alcohols to alkenes?

1 2

Review

Alkenes are Unsaturated IUPAC Nomenclature of Alkenes

 Alkanes have the maximum number of H for its number of 1. Find longest continuous carbon chain that contains the double
carbon atoms: said to be “saturated” bond, for root name
 Molecules with less than the maximum number of H for 2. Number carbons in chain so that both C=C carbons have lowest
the number of carbon atoms are said to be “unsaturated” numbers
 Alkenes are unsaturated

3 4
 Review Review

IUPAC Nomenclature of Alkenes IUPAC Nomenclature of Alkenes

3. Rings have “cyclo” prefix 4. Two double bonds= diene, three double bonds= triene, four=
tetraene … many = polyenes

cyclooctene cyclopropene

Classification terminology:

Is polyethylene a
polyene?

An endocyclic alkene An exocyclic alkene

5 6

Alkene Classifications Alkenes as Substituents

According to substitution: Symmetrical alkene Unsymmetrical alkene

Some
common names: Methylenecyclohexane Vinyl chloride Allyl alcohol

Endocyclic alkene Exocyclic alkene

An allylic alcohol
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 Review Refer to Bruice C1.6-1.7

Bonding in Alkenes Molecular Orbital Description

 MO description of a
C-C bond:

 2 p atomic orbitals
combine to make 2
molecular orbitals (MO)
which are occupied by
 VSEPR: Combination of electrons in two sp2 orbitals of
the electrons
two atoms forms  bond between them
 Additive interaction of p orbitals creates a  bonding
orbital 9 10

Review

Structure of Alkenes Reactivity due to Bonding in Alkenes

 Recall: There are few reactions of alkanes, because C-C and
 Results in alkenes being C-H -bonds are very stable
planar molecules

 Alkenes have C=C double bond functional groups

  bonds are less stable and is a site of reactivity
 Have a higher density of electrons

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 Stabilities of Alkenes Stabilities of Alkenes
 Cis-alkenes are less stable than trans-alkenes because of  The stability of alkenes increases with substitution
steric strain

 Substituents stabilize alkenes by facilitating hyperconjugation

13 14

Hyperconjugation Module H

Alkenes Structure and Reactivity:

Addition via Carbocations
Only those bonds that are aligned Bruice’s Organic Chemistry: Chapters 5-6
H
with the π* orbital and have the
Learning Outcomes:
H
same sign can share electrons by
hyperconjugation 1. What is the characteristic structure and reactivity of alkenes?
2. What is the mechanism and outcome of the addition of HX to alkenes?
 Spreading of electron density from the filled C-H orbital to the 3. What is the stability, reactivity and implications of carbocation intermediates?
C=C antibonding π* orbital 4. What is the mechanism and outcome of the addition of water and alcohols to alkenes?
 The more substituents, the more stabilization by
hyperconjugation is possible
15 16
 Diverse Reactions of Alkenes
Addition of HX

Ether

Haloether 17 18

How to write reaction equations Reaction of Alkenes with HBr

Correct and acceptable:

But this is better: it helps us focus on the organic starting material  Alkenes react with HBr in an overall addition reaction
 Electrophile adds to alkene: an electrophilic addition
 Bromoalkane as product is favored thermodynamically

19 20
 Electrophilic Addition of HX Regioselectivity of Addition
Unsymmetrical
 The addition is Electrophile
general for the
strong HX acids:

Unsymmetrical
Alkene Regioisomers (Constitutional isomers)

 When both reactants are unsymmetrical and add,

constitutional isomer products (regioisomers) are possible
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Regioselectivity of Electrophilic Addition Markovnikov’s Rule

 In the addition of HX to alkenes, the major product results
from the addition of H to the carbon that already has more
H atoms; and X adds to the carbon that has fewer H atoms.
 Example: Two protons on
Major regioisomer this carbon

No protons on
 While there can be two addition outcomes, if one predominates, it this carbon
is said to show regioselectivity
 Summarizing the results of many electrophilic additions of HX to
Not formed!
alkenes, the Russian chemist Vladmir Markovnikov made a Markovnikov Anti-Markovnikov
generalization about the regioselectivity of this reaction, which product product
came to be known as Markovnikov’s rule Regioisomers are a kind of constitutional isomers
23 24
 Markovnikov’s Rule Markovnikov’s Rule
 In the addition of HX to alkenes, the major product results
from the addition of H to the carbon that already has more  But if both carbons of the C=C has the same number of H, then it
follows that there is no selectivity in the addition
H atoms; and X adds to the carbon that has fewer H atoms.
 Example:
One proton One proton
No protons on
on this on this
this carbon
carbon carbon

One proton on this 50% 50%

carbon

25 26

Markovnikov’s Rule Mechanism: Electrophilic Addition of HBr

 General mechanism for all reactions of alkenes:
 The alkene is electron rich due to bond—it is the nucleophile
 The alkene is attracted to the electrophile (electron-deficient species)
and undergoes addition
Markovnikov product Anti-Markovnikov product

 Whenever there should be chaos (multiple outcomes), but there isn’t,

this is called “selectivity”
 Markovnikov’s rule describes the regioselectivity observed in
electrophilic additions of alkenes
 There must be a mechanistic rationale and energy basis for all
selectivities observed  A new electrophile is formed: bromide as a nucleophile adds again
 We need to look for the reasons for selectivity in the mechanism  The addition of HBr is a two step reaction
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 Mechanism: Electrophilic Addition of HBr Module H
 Mechanism showing electron flow:
 Step 1: Electron pair from bond of alkene (Nu:) adds to H+ (E)
Alkenes Structure and Reactivity:
makes carbocation intermediate Addition via Carbocations
“protonation”
Bruice’s Organic Chemistry: Chapters 5-6
Carbocation
Learning Outcomes:
1. What is the characteristic structure and reactivity of alkenes?
2. What is the mechanism and outcome of the addition of HX to alkenes?
 Step 2: Addition of bromide (Nu:) to carbocation (E) makes product 3. What is the stability, reactivity and implications of carbocation intermediates?
4. What is the mechanism and outcome of the addition of water and alcohols to alkenes?

29 30

Electrophilic Addition Reaction Coordinate Diagram Carbocation Intermediate

If the carbocation were to
 In the electrophilic addition, be sp3-hybridized, there is
carbocations are generated as more repulsion between
 Two step reaction bonding pairs of electrons
intermediates
 First step is a protonation
and has highest energy  Tricoordinate carbon is
transition state, thus it is the surrounded by only 6 electrons
slowest and the rate in three bonds in sp2 orbitals Less repulsion
between bonding
determining step  The fourth orbital on carbon is pairs of electrons
 Overall reaction rate is a vacant p-orbital
determined by G1‡ of the  Carbocations are planar
first T. S.
 Carbocations are electron-
deficient (lacking an octet), and
thus unstable, high energy and
reactive!
31 32
 Stereochemistry of HX addition Stereochemistry of HX addition
 Does H+ and Cl - add to the same or opposite faces?
 Both syn (same face)
and anti (opposite face)
addition of HX occurs
to form cis- and trans-
isomers
 If H+ adds from the top, Cl– then adds to the resulting  The addition is non-
carbocation on either the top or the bottom face, since the stereoselective
carbocation is flat
 So HX addition is not stereoselective

33 34

Carbocation Intermediate Carbocation Structure and Stability

Because carbocations are  Carbocations are electron-deficient
electron-deficient, (and  Stability increases with increasing substitution
thus unstable high energy
and reactive), it is
understandable why
Step 2 (carbocation
reaction) is fast!

The carbocation is so
reactive it really wants to
react further to quench
its charge!

35 Less stable Stability More stable 36

 Carbocation Structure and Stability
Carbocation
 Carbocations are Structure and Stability
electron-deficient and Not stabilized
stabilized by A Molecular Orbital Description of
Hyperconjugation
hyperconjugation from
substituents
 The more substituents
there are, the more
hyperconjugation is
possible

37 38

Origin of the Markovnikov Regioselectivity Origin of the Markovnikov Regioselectivity

 Is the reaction regioselective
because reactions always
Tertiary carbocation favour the more stable
intermediate/product?
 No!

 In this case there is no

Primary carbocation
equilibrium between the
alkene and the intermediate,
 The Markovnikov selectivity is determined in the rate determining because the intermediate
step – protonation to form the carbocation continues to a subsequent
 The formation of the more stable carbocation leads to the FAST reaction
Markovnikov addition product
39 40
 Transition State of Rate Determining Step Transition State of Rate Determining Step
Primary carbocation intermediate
Transition state?
G1‡? G1 We call these “early
 The rate of the reaction
transition states”
is related to the G1‡
transition state energy
of the rate determining G1

step (G1‡ vs G1‡), NOT

directly related to the
energy (G1 vs G1) of the
intermediate
 So what do we know
about those transition
states and their We call these “late
energies G1‡ and G1‡? transition states”

41 42

Transition State of Rate Determining Step Transition State of Rate Determining Step
 In the rate determining step, the starting material is the alkene
and the HBr, and the product is the carbocation and Br- -
 The transition state of this step probably has partial C=C breaking and
partial σ C-H bond formation
 But how much bond-breaking/making has occurred—a little, a lot….?
 Is the transition state reactant-like or product-like…?

-
 However, any transition state is transient and cannot be observed!
 A transition state is the highest energy point in a reaction step
 By definition, its structure is not stable enough to exist for one vibration
 If we do not know the transition state structure, we also do not know its G‡

43 44
 The Hammond Postulate A Carbocation-like Transition State
 As applied to the the electrophilic addition:
 The Hammond
Early TS Late TS
Postulate says that we
can infer the transition
state structure from its According to the Hammond
energy Postulate, the transition state of
Transition state not close to
 “The structure of a and does not particularly the rate-determining step should
transition state resemble reactants or products be "carbocation-like"
resembles the stable
species that is nearest
to it in free energy.”

45

46

A Carbocation-like Transition State A Carbocation-like Transition State

 Based on the Hammond postulate, the transition state is more like a
carbocation than an alkene, so C=C bond breaking is quite advanced

Markovnikov
product

carbocation-like transition state

 The more stable carbocation is formed in the RDS, not because the
reaction favours a (thermodynamically) more stable carbocation
intermediate, but because the carbocation-like transition state it goes
through is lower in energy
 Not an alkene-like
transition state!
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 This is the mechanistic rationale for the observed Markovnikov addition selectivity
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 Degrees of Regioselectivity Evidence of Carbocation Intermediates
3° carbocationic TS vs 1° carbocationic TS  How do we know that carbocations really are intermediates
This reaction is more
in this reaction?
regioselective  Some carbocations can be observed, first time in 1901

3° carbocationic TS vs 2° carbocationic TS

 The greater the difference in TS energies, the greater the

difference in the rate of formation of the two carbocations,
the higher the Markovnikov regioselectivity 49 50

Evidence of Carbocation Intermediates Rearrangements of Carbocations

 How do we know that carbocations really are intermediates  Carbocation rearrangements occur by 1,2-hydride shifts
in this reaction? (1,2- is referring to adjacent carbon atoms)
 Carbocations are unstable and they undergo spontaneous
structural rearrangements to transform to more stable carbocations
 This rearrangement behavior is unusual for typical organic
compounds—because stable compounds do not undergo
spontaneous bond-breaking!

H+ = “proton”
H• = “hydrogen atom”
H‫ = ׃‬H − = “hydride”
Isobutyl carbocation Tert-butyl carbocation
Primary carbocation Tertiary carbocation This is a “Hydride” shift: the electron pair moved with the H
51 52
 Rearrangements of Carbocations Rearrangements of Carbocations
 Carbocation rearrangements occur by 1,2-alkyl shifts  Carbocation rearrangements are driven by achieving more
(ie. at adjacent carbon atoms) stability
 No rearrangement occurs if the carbocation does not
Alkyl shifts occur by become more stable
moving the electron pair
with the group

Primary carbocations (since

2
they are so unstable) always
undergo rearrangements to
2 more stable carbocations

53 54

Evidence of Carbocation Intermediates Evidence of Carbocation Intermediates

Markovnikov ???
addition product
It is hard for you to predict how
fast is the rate of direct addition
 How to explain the formation of two products? compared with the rearrangement,
so you should assume both Markovnikov Rearranged
products will be formed. addition product addition product
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 Evidence of Carbocation Intermediates Exercise 1
 Draw the mechanism and derive structures of the major
and minor products.
 What rule/concept SUMMARIZES this selectivity? What
rule/concept EXPLAINS this selectivity?

Again you should assume both ~ 50% yield ~ 50% yield

products would be formed if this Markovnikov Rearranged Pause the video to complete this exercise.
were a test question. addition product addition product
58

Exercise 1 Exercise 2
 Is A a meso compound? Suggest two alkene
starting materials that can synthesize A as a
major product. Is one better than the other for
synthesis? Explain.

Pause the video to complete this exercise.

59 60
Exercise 2 Module H

Alkenes Structure and Reactivity:

Addition via Carbocations
Bruice’s Organic Chemistry: Chapters 5-6

Learning Outcomes:
1. What is the characteristic structure and reactivity of alkenes?
2. What is the mechanism and outcome of the addition of HX to alkenes?
A 3. What is the stability and reactivity of carbocations?
a symmetrical molecule 4. What is the mechanism and outcome of the addition of water and alcohols to alkenes?
but not meso—no
stereocenters
61 62

Module H Other Reactions of Alkenes

Alkenes Structure and Reactivity:
Addition via Carbocations
Bruice’s Organic Chemistry: Chapters 5-6
Ether
Learning Outcomes:
1. What is the characteristic structure and reactivity of alkenes?
2. What is the mechanism and outcome of the addition of HX to alkenes?
3. What is the stability and reactivity of carbocations?
4. What is the mechanism and outcome of the addition of water and alcohols to alkenes?

63 Haloether 64
 Acid-catalyzed Hydration of Alkenes Acid-catalyzed Hydration of Alkenes
 Addition of H-OH to an alkene results in an alcohol
 The reaction is called hydration
 Conversion of ethene to ethanol by hydration is an important
industrial process Markovnikov Anti-Markovnikov
Major Product

 For unsymmetrical alkenes, acid-catalyzed

 Unlike the addition of HX, hydration requires a strong acid
hydration is a Markovnikov addition of water
as catalyst
65 66

Acid-catalyzed Hydration Mechanism Acid-catalyzed Hydration Mechanism

 A three-step reaction:
Step 1 Step 2 Step 3
 Step 1: Electrophilic addition of alkene to H+ H H
 Step 2: H2O adds to carbocation intermediate O

 Step 3: Deprotonation to give alcohol (regenerate H+ catalyst)

H H
O

 In Step 1, water itself does not ionize to produce enough protons;

therefore an acid catalyst is needed
 The more stable carbocation is formed, leading to a Markovnikov
addition
 In Step 2, the most abundant nucleophile, water, adds
 Step 3 occurs to make neutral alcohol product
67 68
Hydration Reaction Coordinate Diagram Acid-catalyzed Addition of Alcohols
 A similar acid-catalyzed addition of alcohol to an alkene
 A three-step reaction occurs when the reaction is conducted in alcohol as
with two intermediates
solvent (instead of water)
 Step 1 is rate
determining step  Results in ethers as products
FREE ENERGY

 Carbocation is an
intermediate
 Similarities to HX
addition
 Step 2 and 3 are
comparatively fast

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70

Acid-catalyzed Addition of Alcohols Stereochemistry of Hydration

 Very similar mechanism, just a different nucleophile  Hydration can create a stereocenter and result in chiral
alcohols as products
 The addition of HO-H or RO-H is non-stereoselective: both
syn and anti additions are possible

71 72
Achiral Intermediates Give Racemic Products Problems in Acid-catalyzed Hydration
 Protonation of alkene gives planar, achiral carbocation:
top and bottom face addition are equally accessible by H2O

Results in a mixture!

 Because carbocations are intermediates in acid-catalyzed hydration,

undesired alcohol products resulting from rearrangements (and
therefore mixtures of products) are possible, sometimes inevitable
 This reaction is a good procedure only for the synthesis of simple
alcohols, or alcohols from carbocations that do not rearrange
73 74

Exercise 3 Exercise 3
 What is the full IUPAC name of B? Is the
indicated reaction selective for forming one cat. H2SO4
4 3 2 CH3OH
product? If not, what are the possible products?
5 1
Show by drawing a detailed mechanism. 6
 Would the reaction outcome be improved by the B (R)-3-methylcyclohex-1-ene
use of HCl as catalyst? Why or why not?

Pause the video to complete this exercise.

75 76
 Exercise 4 Exercise 4
 Suggest two alkene starting materials to synthesize  Suggest two alkene starting materials to synthesize
hexan-3-ol. hexan-3-ol.

Pause the video to complete this exercise.

77 78

Summary: Electrophilic addition of HX and H2O Summary: Carbocations

 Alkenes are electron-rich: act as -nucleophiles toward
protons of strong acids, eg. HCl, HBr, HI, H2SO4, H3PO4  Reactive intermediates!
 Multi-step mechanism  Relative stabilities:
 1. Addition of H+ to form carbocation: rate determining step tertiary > secondary > primary >> methyl
 Proceeds via the more stable carbocation-like transition state
 Rearrangements of carbocation intermediate are possible
 2. Addition of X− or H2O or ROH
 The Hammond Postulate proposes a carbocation-like
(not alkene-like) transition state for the rate determining
 3. For neutral nucleophiles (H2O or ROH), a final deprotonation step
step of electrophilic addition of protons
is needed to return product to neutrality
 Less stable carbocations rearrange to more stable
 Addition is regioselective (Markovnikov) but not stereoselective carbocations via 1,2-hydride or 1,2-alkyl shifts
79 80
Module H

Alkenes Structure and Reactivity:

Addition via Carbocations
Bruice’s Organic Chemistry: Chapters 5-6

Check that you have achieved these learning outcomes, and can give
examples to explain and answer each of these questions:
1. What is the characteristic structure and reactivity of alkenes?
2. What is the mechanism and outcome of the addition of HX to alkenes?
3. What is the stability, reactivity and implications of carbocation intermediates?
4. What is the mechanism and outcome of the addition of water and alcohols to alkenes?

81