Chapter 9 Addition Reactions of Alkenes '13 BW

9.1 Addition Reactions: A Pi Bond is Converted to a Sigma Bond!
Chapter 9. Addition Reactions of Alkenes! ! "

Junha Jeon !
Department of Chemistry ! University of Texas at Arlington ! Arlington, Texas 76019 ! " ! Chem 2321, Fall 123 !
Various Addition Reactions!
Various Addition Reactions!
9.2 Addition vs. Elimination: Thermodynamics!
Addition vs. Elimination: A Thermodynamic Perspective!
in equilibrium (thermodynamics) ! !
1 !
9.3 Hydrohalogenation!
2 !
Hydrohalogenation!
9.3 Hydrohalogenation! Markovnikov Addition !
Regiochemistry!! !

! Hydrogen tends to add to the carbon already bearing more H atoms. ! !

! Hydrogen tends to add to the carbon already bearing more H atoms. ! !
Hydrohalogenation! Markovnikov Addition !

! Halogen is generally placed at the more substituted position.!
Hydrohalogenation! Markovnikov Addition !

! Halogen is generally placed at the more substituted position.!
Regioselective! !
3 !
Hydrohalogenation!
Of course, "
Hydrohalogenation!
Anti-Markovnikov Addition !
!
in Chapter 11 !
Mechanism of Hydrohalogenation" !
Mechanism of Hydrohalogenation" !
Two Mechanistic Pathways!
4 !
Mechanistic Pathways! Which transition state (TS) is ! more stable? And why?!
Mechanistic Pathways! Which transition state (TS) is ! more stable? And why?" Hammond Postulate"
Recall the Hammond Postulate!

The structure of a transition state resembles the structure of the nearest stable species. Transition states for endergonic steps structurally resemble products, and transition states for exergonic steps structurally resemble reactants.!
Mechanistic Pathways! Which transition state (TS) is ! more stable? And why?" Hammond Postulate"
Mechanistic Pathways!
5 !
Ionic Stepwise Reaction: Markovnikov Addition (Regioselectivity)!
The take home message is that the regioselectivity of an ionic addition

carbocation! characters!
reaction is determined by the preference for the reaction to proceed

carbocation! characters ! more stable carbocation intermediate: Markovnikov addition ! through the
Ea!
Stereochemistry of Hydrohalogenation!
The take home message is that the regioselectivity of an ionic addition reaction is determined by the preference for the reaction to proceed
carbocation! characters ! more stable carbocation intermediate: Markovnikov addition ! through the Markovnikov Addition: ! ! Hydrogen tend to add to the carbon already bearing more H atoms.! ! Halogen is generally placed at the more substituted position.!
Stereochemistry of Hydrohalogenation!
Stereochemistry: Carbocation Intermediate!
Two enantiomers as a racemic mixture are produced!
6 !
Hydrohalogenation with Carbocation Rearrangement!
9.4 Acid-Catalyzed Hydration!
Acid-Catalyzed Hydration!
7 !
Acid-Catalyzed Hydration: Markovnikov Addition!
Mechanism and Source of Regioselectivity!
Recall: Addition vs. Elimination: A Thermodynamic Perspective!
Le Chateliers Principle:! If a chemical system at equilibrium experiences a change in concentration, " temperature, volume, or partial pressure, then the equilibrium shifts to " counteract the imposed change and a new equilibrium is established.!
Acid-Catalyzed Hydration: Stereochemistry Observation!
Recall Stereochemistry: Carbocation Intermediate!
8 !
9.5 Oxymercuration Demercuration: Carbocation Rearrangement!
9.5 Oxymercuration Demercuration: Carbocation Rearrangement!
H3O+ + OH
as a mixture!
OH
9.5 Oxymercuration Demercuration!

The Periodic Table of the Elements
1
Hydrogen
Oxymercuration Demercuration!
18 1
Hydrogen
18
Alkali metals Alkaline earth metals Transition metals Other metals Metalloids (semi-metal) Nonmetals Halogens Noble gases
H
1.01
Lithium
2
Beryllium
Li
6.94
Sodium
Be
9.01
Magnesium
Element name Symbol
Mercury
Helium
80
Atomic #
13
Boron
Element name Symbol
Mercury
Helium
He
14
Carbon
H
1.01
Lithium
Hg
200.59
Avg. Mass
15
Nitrogen
16
Oxygen
17
Fluorine
4.00
Neon
2
Beryllium
80
Atomic #
13
Boron
He
14
Carbon
10
Hg
200.59
Avg. Mass
15
Nitrogen
16
Oxygen
17
Fluorine
4.00
Neon
10
B
10.81
Aluminum
C
12.01
Silicon
N
14.01
Phosphorus
O
16.00
Sulfur
F
19.00
Chlorine
Ne
20.18
Argon
Li
6.94
Sodium
Be
9.01
Magnesium
B
10.81
Aluminum
C
12.01
Silicon
N
14.01
Phosphorus
O
16.00
Sulfur
F
19.00
Chlorine
Ne
20.18
Argon
11
12
13
14
15
16
17
18
11
12
13
14
15
16
17
18
Na
22.99
Potassium
Mg
24.31 3
Calcium Scandium
Al
26.98 4
Titanium
Si
28.09
Germanium
P
30.97
Arsenic
S
32.07
Selenium
Cl
35.45
Bromine
Ar
39.95
Krypton
Na
22.99
Potassium
Mg
24.31 3 4
Titanium
Al
26.98 5
Vanadium
Si
28.09
Germanium
P
30.97
Arsenic
S
32.07
Selenium
Cl
35.45
Bromine
Ar
39.95
Krypton
5
Vanadium
6
Chromium
7
Manganese
8
Iron
9
Cobalt
10
Nickel
11
Copper
12
Zinc Gallium Calcium
6
Chromium
7
Manganese
8
Iron
9
Cobalt
10
Nickel
11
Copper
12
Zinc Gallium
Scandium
19
K
39.10
Rubidium
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
19
Ca
40.08
Strontium
Sc
44.96
Yttrium
Ti
47.88
Zirconium
V
50.94
Niobium
Cr
52.00
Molybdenum
Mn
54.94
Technetium
Fe
55.85
Ruthenium
Co
58.93
Rhodium
Ni
58.69
Palladium
Cu
63.55
Silver
Zn
65.39
Cadmium
Ga
69.72
Indium
Ge
72.61
Tin
As
74.92
Antimony
Se
78.96
Tellurium
Br
79.90
Iodine
Kr
83.80
Xenon
K
39.10
Rubidium
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
Ca
40.08
Strontium
Sc
44.96
Yttrium
Ti
47.88
Zirconium
V
50.94
Niobium
Cr
52.00
Molybdenum
Mn
54.94
Technetium
Fe
55.85
Ruthenium
Co
58.93
Rhodium
Ni
58.69
Palladium
Cu
63.55
Silver
Zn
65.39
Cadmium
Ga
69.72
Indium
Ge
72.61
Tin
As
74.92
Antimony
Se
78.96
Tellurium
Br
79.90
Iodine
Kr
83.80
Xenon
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
Rb
85.47
Cesium
Sr
87.62
Barium
Y
88.91
Lutetium
Zr
91.22
Hafnium
Nb
92.91
Tantalum
Mo
95.94
Tungsten
Tc
(98)
Rhenium
Ru
101.07
Osmium
Rh
102.91
Iridium
Pd
106.42
Platinum
Ag
107.87
Gold
Cd
112.41
Mercury
In
114.82
Thallium
Sn
118.71
Lead
Sb
121.76
Bismuth
Te
127.60
Polonium
I
126.90
Astatine
Xe
131.29
Radon
Rb
85.47
Cesium
Sr
87.62
Barium
Y
88.91
Lutetium
Zr
91.22
Hafnium
Nb
92.91
Tantalum
Mo
95.94
Tungsten
Tc
(98)
Rhenium
Ru
101.07
Osmium
Rh
102.91
Iridium
Pd
106.42
Platinum
Ag
107.87
Gold
Cd
112.41
Mercury
In
114.82
Thallium
Sn
118.71
Lead
Sb
121.76
Bismuth
Te
127.60
Polonium
I
126.90
Astatine
Xe
131.29
Radon
55
56
Cs
132.91
Francium
Ba
137.33
Radium
57-70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
55
56
Lu
174.97
Lawrencium
Hf
178.49
Rutherfordium
Ta
180.95
Dubnium
W
183.84
Seaborgium
Re
186.21
Bohrium
Os
190.23
Hassium
Ir
192.22
Meitnerium
Pt
195.08
Darmstadtium
Au
196.97
Roentgenium
Hg
200.59
Copernicium
Tl
204.38
Ununtrium
Pb
207.20
Ununquadium
Bi
208.98
Ununpentium
Po
(209)
Ununhexium
At
(210)
Ununseptium
Rn
(222)
Ununoctium
Cs
132.91
Francium
Ba
137.33
Radium
57-70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
Lu
174.97
Lawrencium
Hf
178.49
Rutherfordium
Ta
180.95
Dubnium
W
183.84
Seaborgium
Re
186.21
Bohrium
Os
190.23
Hassium
Ir
192.22
Meitnerium
Pt
195.08
Darmstadtium
Au
196.97
Roentgenium
Hg
200.59
Copernicium
Tl
204.38
Ununtrium
Pb
207.20
Ununquadium
Bi
208.98
Ununpentium
Po
(209)
Ununhexium
At
(210)
Ununseptium
Rn
(222)
Ununoctium
87
88
Fr
(223)
Ra
(226)
89-102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
87
88
**
Lr
(262)
Rf
(267)
Db
(268)
Sg
(271)
Bh
(272)
Hs
(270)
Mt
(276)
Ds
(281)
Rg
(280)
Cn
(285)
Uut
(284)
Uuq
(289)
Uup
(288)
Uuh
(293)
Uus
(294?)
Uuo
(294)
Fr
(223)
Ra
(226)
89-102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
**
Lr
(262)
Rf
(267)
Db
(268)
Sg
(271)
Bh
(272)
Hs
(270)
Mt
(276)
Ds
(281)
Rg
(280)
Cn
(285)
Uut
(284)
Uuq
(289)
Uup
(288)
Uuh
(293)
Uus
(294?)
Uuo
(294)
Lanthanum
Cerium
Praseodymium
Neodymium
Promethium
Samarium
Europium
Gadolinium
Terbium
Dysprosium
Holmium
Erbium
Thulium
Ytterbium
Lanthanum
Cerium
Praseodymium
Neodymium
Promethium
Samarium
Europium
Gadolinium
Terbium
Dysprosium
Holmium
Erbium
Thulium
Ytterbium
*lanthanides
57
58
59
60
61
62
63
64
65
66
67
68
69
70
La
138.91
Actinium
Ce
140.12
Thorium
Pr
140.91
Protactinium
Nd
144.24
Uranium
Pm
(145)
Neptunium
Sm
150.36
Plutonium
Eu
151.97
Americium
Gd
157.25
Curium
Tb
158.93
Berkelium
Dy
162.50
Californium
Ho
164.93
Einsteinium
Er
167.26
Fermium
Tm
168.93
Mendelevium
Yb
173.04
Nobelium
*lanthanides
57
58
59
60
61
62
63
64
65
66
67
68
69
70
La
138.91
Actinium
Ce
140.12
Thorium
Pr
140.91
Protactinium
Nd
144.24
Uranium
Pm
(145)
Neptunium
Sm
150.36
Plutonium
Eu
151.97
Americium
Gd
157.25
Curium
Tb
158.93
Berkelium
Dy
162.50
Californium
Ho
164.93
Einsteinium
Er
167.26
Fermium
Tm
168.93
Mendelevium
Yb
173.04
Nobelium
**actinides
89
90
91
92
93
94
95
96
97
98
99
100
101
102
Ac
(227)
Th
232.04
Pa
231.04
U
238.03
Np
(237)
Pu
(244)
Am
(243)
Cm
(247)
Bk
(247)
Cf
(251)
Es
(252)
Fm
(257)
Md
(258)
No
(259)
**actinides
89
90
91
92
93
94
95
96
97
98
99
100
101
102
Ac
(227)
Th
232.04
Pa
231.04
U
238.03
Np
(237)
Pu
(244)
Am
(243)
Cm
(247)
Bk
(247)
Cf
(251)
Es
(252)
Fm
(257)
Md
(258)
No
(259)
a powerful electrophile!
9 !
1
Hydrogen
18
Element name Symbol
Mercury
Helium
H
1.01
Lithium
2
Beryllium
80
Atomic #
13
Boron
He
14
Carbon
Hg
200.59
Avg. Mass
15
Nitrogen
16
Oxygen
17
Fluorine
4.00
Neon
10
Li
6.94
Sodium
Be
9.01
Magnesium
B
10.81
Aluminum
C
12.01
Silicon
N
14.01
Phosphorus
O
16.00
Sulfur
F
19.00
Chlorine
Ne
20.18
Argon
11
12
13
14
15
16
17
18
Na
22.99
Potassium
Mg
24.31 3
Calcium Scandium
Al
26.98 4
Titanium
Si
28.09
Germanium
P
30.97
Arsenic
S
32.07
Selenium
Cl
35.45
Bromine
Ar
39.95
Krypton
5
Vanadium
6
Chromium
7
Manganese
8
Iron
9
Cobalt
10
Nickel
11
Copper
12
Zinc Gallium
19
K
39.10
Rubidium
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
Ca
40.08
Strontium
Sc
44.96
Yttrium
Ti
47.88
Zirconium
V
50.94
Niobium
Cr
52.00
Molybdenum
Mn
54.94
Technetium
Fe
55.85
Ruthenium
Co
58.93
Rhodium
Ni
58.69
Palladium
Cu
63.55
Silver
Zn
65.39
Cadmium
Ga
69.72
Indium
Ge
72.61
Tin
As
74.92
Antimony
Se
78.96
Tellurium
Br
79.90
Iodine
Kr
83.80
Xenon
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
Rb
85.47
Cesium
Sr
87.62
Barium
Y
88.91
Lutetium
Zr
91.22
Hafnium
Nb
92.91
Tantalum
Mo
95.94
Tungsten
Tc
(98)
Rhenium
Ru
101.07
Osmium
Rh
102.91
Iridium
Pd
106.42
Platinum
Ag
107.87
Gold
Cd
112.41
Mercury
In
114.82
Thallium
Sn
118.71
Lead
Sb
121.76
Bismuth
Te
127.60
Polonium
I
126.90
Astatine
Xe
131.29
Radon
55
56
Cs
132.91
Francium
Ba
137.33
Radium
57-70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
Lu
174.97
Lawrencium
Hf
178.49
Rutherfordium
Ta
180.95
Dubnium
W
183.84
Seaborgium
Re
186.21
Bohrium
Os
190.23
Hassium
Ir
192.22
Meitnerium
Pt
195.08
Darmstadtium
Au
196.97
Roentgenium
Hg
200.59
Copernicium
Tl
204.38
Ununtrium
Pb
207.20
Ununquadium
Bi
208.98
Ununpentium
Po
(209)
Ununhexium
At
(210)
Ununseptium
Rn
(222)
Ununoctium
87
88
Fr
(223)
Ra
(226)
89-102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
**
Lr
(262)
Rf
(267)
Db
(268)
Sg
(271)
Bh
(272)
Hs
(270)
Mt
(276)
Ds
(281)
Rg
(280)
Cn
(285)
Uut
(284)
Uuq
(289)
Uup
(288)
Uuh
(293)
Uus
(294?)
Uuo
(294)
Lanthanum
Cerium
Praseodymium
Neodymium
Promethium
Samarium
Europium
Gadolinium
Terbium
Dysprosium
Holmium
Erbium
Thulium
Ytterbium
*lanthanides
57
58
59
60
61
62
63
64
65
66
67
68
69
70
La
138.91
Actinium
Ce
140.12
Thorium
Pr
140.91
Protactinium
Nd
144.24
Uranium
Pm
(145)
Neptunium
Sm
150.36
Plutonium
Eu
151.97
Americium
Gd
157.25
Curium
Tb
158.93
Berkelium
Dy
162.50
Californium
Ho
164.93
Einsteinium
Er
167.26
Fermium
Tm
168.93
Mendelevium
Yb
173.04
Nobelium
**actinides
89
90
91
92
93
94
95
96
97
98
99
100
101
102
Ac
(227)
Th
232.04
Pa
231.04
U
238.03
Np
(237)
Pu
(244)
Am
(243)
Cm
(247)
Bk
(247)
Cf
(251)
Es
(252)
Fm
(257)
Md
(258)
No
(259)
OxymercurationDemercuration:! ! 1. Markovnikov Addition! ! 2. Not readily undergo carbocation rearrangements!
OxymercurationDemercuration:! ! 1. Markovnikov Addition! ! 2. Not readily undergo carbocation rearrangements! (c.f. acid-catalyzed hydration)!
Demercuration by sodium borohydride is believed to occur via a radical process.!
10 !
9.6 HydroborationOxidation!
1. Regioselectivity: Anti-Markovnikov Addition!
OxymercurationDemercuration:! ! 1. Markovnikov Addition! ! 2. Not readily undergo carbocation rearrangements!
2. Stereospecicity: Syn Addition!
9.6 HydroborationOxidation!
1. Regioselectivity: Anti-Markovnikov Addition! 2. Stereospecicity: Syn Addition!
HydroborationOxidation: Boron Isoelectronic to Carbocation!
CH3+!
BH3!
The BH3 molecule is similar to a carbocation but not as reactive, ! because it does not carry a formal charge.!
Diborane!
The BH3 molecule is similar to a carbocation but not as reactive, because it does not carry a formal charge. But, ! because of their broken octet, BH3 molecules is still reactive and undergo intermolecular resonance to help fulll their octets.! !
Diborane!
The BH3 molecule is similar to a carbocation but not as reactive, because it does not carry a formal charge. But, ! because of their broken octet, BH3 molecules is still reactive and undergo intermolecular resonance to help fulll their octets.! !
11 !
Diborane: Three-center, Two-electron Bonds!
Stabilizing Borane: Diborane via Three-center, Two-electron Bonds!
H B H H
H + H B H
H B H
H B H
H H
Three-center, Two-electron Bonds!
Stabilizing Borane: Ate Complex!
HydroborationOxidation: Mechanism!
HydroborationOxidation: Mechanism!
HydroborationOxidation: Mechanism Electronic Considerations!

1.Regioselectivity: Anti-Markovnikov Addition! 2. Stereospecicity: Syn Addition!
12 !
HydroborationOxidation: Mechanism Steric Considerations!
Oxidation Mechanism!
HydroborationOxidation: Stereochemistry!
HydroborationOxidation: Stereochemistry!
to the board!
13 !
9.7 Catalytic Hydrogenation!
Catalytic Hydrogenation: Stereospecicity!

# The addition of H2 across a C=C double bond:!
# If a chirality center is formed, SYN addition is observed.!
Catalytic Hydrogenation: The Role of the Catalyst!
Catalytic Hydrogenation: Catalysts Pt, Pd, Ni!
Catalytic Hydrogenation: Catalysts Pt, Pd, Ni Yes, IRONMAN!!!
Pt, Pd, NiPalladium Arc Reactor!
14 !
Pt, Pd, NiPalladium Arc ReactorAre you kidding?!
Molecular Hydrogen Bound to Catalyst and Breaking HH bonds!
Alkene Bound to Catalyst!
One H Atom Tranfer: Partially Reduced Intermediate!
A Second H Transfer: Fully Reduced Alkene Syn Addition!
Homogeneous Catalysts!
15 !
Skip this section: A Chiral Phosphine Ligand!
Skip this section: Asymmetric Hydrogenation!
Skip this section: Asymmetric Hydrogenation!
9.8 Halogenation and Halohydrin Formation!
O OH HO OH NH2
catalyst H2 HO OH
(S)
O OH
NH2
L-dopa for Parkinson's disease
16 !
Halogenation!
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 stereospecicity, is it likely to be a concerted or a multi-step process?!
# 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 stereospecicity, is it likely to be a concerted or a multi-step process?!
Halogenation!
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 stereospecicity, is it likely to be a concerted or a multi-step process?!
# 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 stereospecicity, is it likely to be a concerted or a multi-step process?!
Halogenation: London Dispersion Forces (Induced Dipole Moment)!
Halogenation: London Dispersion Forces (Induced Dipole Moment)!
17 !
Halogenation Should be Anti Addition???!
Halogenation: Formation of Bromonium Ion!
Halogenation: Anti Addition!
Halogenation: Anti Addition!
Stereochemistry: E and Z alkenes!
Stereochemistry: E and Z alkenes!
18 !
Halohydrin: Intercepting the Bromonium Intermediate!

# 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.!
Halohydrin: Intercepting the Bromonium Intermediate!
Halohydrin!
Halohydrin: Regioselectivity!
19 !
Halohydrin: Regioselectivity Stable Transition State: Partial C+!
Halohydrin: Regioselectivity Stable Transition State: Steric?!
Water is a small molecule that can easily access the more sterically hindered site.! !
9.9 Anti Dihydroxylation"
Anti Dihydroxylation"
Anti Dihydroxylation"
Formation of an Epoxide!
# Replacing the relatively unstable OO single bond is the thermodynamic driving force for this process.!
20 !
Peroxy Acid (RCO3H)!
Formation of an Epoxide!
Water is a poor nucleophile, so the epoxide is activated with an acid.! # Replacing the relatively unstable OO single bond is the thermodynamic driving force for this process.!
Key Intermediates!
9.10 Syn Dihydroxylaton: Concerted Process"
Syn Dihydroxylaton"
Syn Dihydroxylaton"
# Because OsO4 is expensive and toxic, conditions have been developed where the OsO4 is regenerated after reacting, so only catalytic amounts are needed. !
21 !
Syn Dihydroxylaton"
9.11 Oxidative Cleavage of Alkenes by Ozonolysis!
# 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.!
Ozone exists as a resonance hybrid of two contributors!
Common reducing agents include dimethyl sulde (Me2S) and Zn. !
Example of Ozonolysis!
1) O3 2) DMS (Me2S)
O O H
Common reducing agents include dimethyl sulde (Me2S) and Zn. !
22 !
1) O3 2) DMS (Me2S)
O O H
1) O3 2) DMS (Me2S)
O O H
Predicting the Products of an Addition Reaction!

1.# What are the identities of the groups being added the double bond?! 2.# What is the expected regioselectivity (Markovnikov or anti-Markovnikov addition)?! 3.# What is the expected stereospecicity (syn or anti addition)?!


9.13 Synthesis Strategies: One-Step Syntheses!
23 !
Synthesis Strategies: One-Step Syntheses!
Synthesis Strategies: One-Step Syntheses!
Synthesis Strategies: Multi-Step Syntheses! !# Changing the position of a leaving group! ! ! ! ! ! ! ! !

What are our weapons?! ! 1. Substitution reactions! 2. Elimination reactions! 3. Addition reactions !



24 !
A Choice of Reagents! ! ! ! ! ! ! ! !
! 1. Substitution reactions! 2. Elimination reactions! 3. Addition reactions !
Hydrohalogenation! !# Changing the position of a leaving group! ! ! ! ! ! ! ! !

Synthesis Strategies: Multi-Step Syntheses Example !
Synthesis Strategies: Multi-Step Syntheses Example !
Synthesis Strategies: Multi-Step Syntheses! !# Changing the position of a $ bond! ! ! ! ! ! ! ! !
25 !

Chapter 9 Addition Reactions of Alkenes '13 BW

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Chapter 9 Addition Reactions of Alkenes '13 BW

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9.1 Addition Reactions: A Pi Bond is Converted to a Sigma Bond!

Chapter 9. Addition Reactions of Alkenes! ! "

Various Addition Reactions!

Various Addition Reactions!

9.2 Addition vs. Elimination: Thermodynamics!

Addition vs. Elimination: A Thermodynamic Perspective!

Addition vs. Elimination: A Thermodynamic Perspective!

Addition vs. Elimination: A Thermodynamic Perspective!

Addition vs. Elimination: A Thermodynamic Perspective!

Addition vs. Elimination: A Thermodynamic Perspective!

Addition vs. Elimination: A Thermodynamic Perspective!

9.3 Hydrohalogenation! Markovnikov Addition !

9.3 Hydrohalogenation! Markovnikov Addition !

9.3 Hydrohalogenation! Markovnikov Addition !

Hydrohalogenation! Markovnikov Addition !

Hydrohalogenation! Markovnikov Addition !

Two Mechanistic Pathways!

Two Mechanistic Pathways!

Two Mechanistic Pathways!

Recall the Hammond Postulate!

Ionic Stepwise Reaction: Markovnikov Addition (Regioselectivity)!

Ionic Stepwise Reaction: Markovnikov Addition (Regioselectivity)!

The take home message is that the regioselectivity of an ionic addition

reaction is determined by the preference for the reaction to proceed

Ionic Stepwise Reaction: Markovnikov Addition (Regioselectivity)!

Stereochemistry: Carbocation Intermediate!

Two enantiomers as a racemic mixture are produced!

Hydrohalogenation with Carbocation Rearrangement!

Hydrohalogenation with Carbocation Rearrangement!

Hydrohalogenation with Carbocation Rearrangement!

9.4 Acid-Catalyzed Hydration!

Acid-Catalyzed Hydration: Markovnikov Addition!

Mechanism and Source of Regioselectivity!

Recall: Addition vs. Elimination: A Thermodynamic Perspective!

Acid-Catalyzed Hydration: Stereochemistry Observation!

Recall Stereochemistry: Carbocation Intermediate!

9.5 Oxymercuration Demercuration: Carbocation Rearrangement!

9.5 Oxymercuration Demercuration: Carbocation Rearrangement!

9.5 Oxymercuration Demercuration!

Element name Symbol

Element name Symbol

Element name Symbol

OxymercurationDemercuration:! ! 1. Markovnikov Addition! ! 2. Not readily undergo carbocation rearrangements!

Demercuration by sodium borohydride is believed to occur via a radical process.!

OxymercurationDemercuration:! ! 1. Markovnikov Addition! ! 2. Not readily undergo carbocation rearrangements!

2. Stereospecicity: Syn Addition!

HydroborationOxidation: Boron Isoelectronic to Carbocation!

Diborane: Three-center, Two-electron Bonds!

Stabilizing Borane: Diborane via Three-center, Two-electron Bonds!

Three-center, Two-electron Bonds!

Stabilizing Borane: Ate Complex!

1. Regioselectivity: Anti-Markovnikov Addition! 2. Stereospecicity: Syn Addition!

HydroborationOxidation: Mechanism Electronic Considerations!

HydroborationOxidation: Mechanism Steric Considerations!

1. Regioselectivity: Anti-Markovnikov Addition! 2. Stereospecicity: Syn Addition!

9.7 Catalytic Hydrogenation!

Catalytic Hydrogenation: Stereospecicity!

# If a chirality center is formed, SYN addition is observed.!

Catalytic Hydrogenation: The Role of the Catalyst!

Catalytic Hydrogenation: Catalysts Pt, Pd, Ni!

Catalytic Hydrogenation: Catalysts Pt, Pd, Ni Yes, IRONMAN!!!

Pt, Pd, NiPalladium Arc Reactor!

Pt, Pd, NiPalladium Arc ReactorAre you kidding?!