Alkenes 11-1 Naming the Alkenes

1 2

Naming the Alkenes: IUPAC Rules Naming the Alkenes: IUPAC Rules

3 4
 Naming the Alkenes: IUPAC Rules Naming the Alkenes: IUPAC Rules

5 6

11-2 Structure and Bonding in Ethene: The Pi Bond Structure and Bonding in Ethene: The C–C Sigma Bond

7 8
Structure and Bonding in Ethene: The C–C Pi Bond Structure and Bonding in Ethene: The C–C Pi Bond

9 10

11-3 Physical Properties of Alkenes Physical Properties of Alkenes: Acidity of Ethenyl Hydrogen

11 12
 11-4 Nuclear Magnetic Resonance of Alkenes Nuclear Magnetic Resonance of Alkenes

The pi electrons exert a deshielding effect on alkenyl hydrogens13 The pi electrons exert a deshielding effect on alkenyl hydrogens14

Nuclear Magnetic Resonance of Alkenes: Cis- vs Trans- Nuclear Magnetic Resonance of Alkenes: Cis- vs Trans-

Jcis is about 6-14 Hz 15 Jtrans is about 11-18 Hz 16

NMR of Alkenes: Coupling Constants Around a Double Bond NMR of Alkenes: Coupling Constants Around a Double Bond

17 18

NMR of Alkenes: Coupling Constants-Combining Effects NMR of Alkenes: Coupling Constants-Combining Effects

19 20
 NMR of Alkenes: Deshielded in 13C NMR Hydrogenation of Alkenes: Relative Stability of C=C Bonds

21 22

Hydrogenation of Alkenes: Relative Stability of C=C Bonds Hydrogenation of Alkenes: Relative Stability of C=C Bonds

23 24
Hydrogenation of Alkenes: Relative Stability of C=C Bonds 11-6 Preparation of Alkenes from Alkyl Halides and Sulfonates

25 26

Elimination of Alkyl Halides: The Effects of Bases Elimination of Alkyl Halides: The Saytzev Rule

27 28
Elimination of Alkyl Halides: The Hofmann Rule Elimination of Alkyl Halides: Working with the Concept

29 30

Elimination of Alkyl Halides: Trans- over Cis- Elimination of Alkyl Halides: Stereospecific E2

31 32
Elimination of Alkyl Halides: Stereospecific E2 11-7 Preparation of Alkenes by Dehydration of Alcohols

33 34

Dehydration of Alcohols: Relative Reactivity Dehydration of Alcohols: Rearrangement

35 36
 11-8 Infrared Spectroscopy 11-8 Infrared Spectroscopy

37 38

Infrared Spectroscopy: Molecular Vibrations Infrared Spectroscopy: Molecular Vibrations

39 40
Infrared Spectroscopy: Stretching Wavenumber Ranges Infrared Spectroscopy: Examples

41 42

Infrared Spectroscopy: Examples Infrared Spectroscopy: Examples

43 44
Infrared Spectroscopy: Examples Infrared Spectroscopy: IR of Bending Modes of Alkenes

45 46

11-9 Mass Spectroscopy Mass Spectroscopy: Ionization of a Molecule

47 48
High-Resolution Mass Spectroscopy: Molecular Formulas Mass Spectroscopy: Ionization of a Molecule

49 50

Mass Spectroscopy: Molecular Ion Fragmentation Mass Spectroscopy: Molecular Ion Fragmentation

51 52
Mass Spectroscopy: Presence of Isotopes 11-10 Fragmentation Patterns of Organic Molecules

53 54

Fragmentation Patterns: n-Pentane Case Fragmentation Patterns: 2-Methylbutane Case

55 56
 Fragmentation Patterns: 2-Methylbutane Case Fragmentation Patterns: 2,2-Dimethylpropane Case

57 58

Fragmentation Patterns: 2,2-Dimethylpropane Case Fragmentation Patterns: Identify Functional Groups

59 60
Fragmentation Patterns: Identify Functional Groups Fragmentation Patterns: Identify Functional Groups

61 62

Fragmentation Patterns: Identify Functional Groups Fragmentation Patterns: Identify Functional Groups

63 64
 Fragmentation Patterns: Identify Functional Groups 11-11 Degree of Unsaturation

The degree of unsaturation is the sum of the numbers of rings and π bonds
65 66
present in the molecule.

Degree of Unsaturation: How to Calculate? Exercises

The degree of unsaturation is the sum of the numbers of rings and π bonds
67 68
present in the molecule.
 Solving Problems in Organic Chemistry

69 70

Solving Problems in OrgChem: Understanding the Question Solving Problems in OrgChem: The WHIP Strategy

71 72
Solving Problems That Ask “How?” and/or “Why?” Solving Problems That Ask “How?” and/or “Why?”

73 74

Solving Problems That Ask “How?” and/or “Why?” Solving Problems That Ask “How?” and/or “Why?”

75 76
Solving Problems That Ask “How?” and/or “Why?” Solving Problems That Ask “How?” and/or “Why?”

77 78

Reactions of Alkenes 12-1 Why Addition Reactions Proceed: Thermodynamic

79 80
12-1 Why Addition Reactions Proceed: Thermodynamic 12-1 Why Addition Reactions Proceed: Thermodynamic

81 82

12-2 Catalytic Hydrogenation Catalytic Hydrogenation: Heterogeneous Catalysis

83 84
Catalytic Hydrogenation: Homogeneous Catalysis Homogeneous Catalysis: Mechanism

85 86

Homogeneous Catalysis: Mechanism Catalytic Hydrogenation: Stereospecific

87 88
 Catalytic Hydrogenation: Stereospecific 12-3 Electrophilic Addition of Hydrogen Halides

89 90

Electrophilic Addition of Hydrogen Halides EA of Hydrogen Halides: Markovnikov Rule

91 The key is the relative stability of the resulting carbocation intermediates.

92
 EA of Hydrogen Halides: Markovnikov Rule EA of Hydrogen Halides: Markovnikov Rule

The key is the relative stability of the resulting carbocation intermediates.

93 The initial protonation gives the more stable carbocation. 94

EA of Hydrogen Halides: Carbocation Rearrangements 12-4 Alcohol Synthesis by Electrophilic Hydration

95 96
Alkene Hydration vs Alcohol Dehydration: Equilibrium Processes Alkene Hydration vs Alcohol Dehydration: Equilibrium Processes

97 98

Alkene Hydration vs Alcohol Dehydration: Equilibrium Processes 12-5 Electrophilic Addition of Halogens to Alkenes

99 100
Electrophilic Addition of Halogens to Alkenes: Anti Additon Electrophilic Addition of Halogens to Alkenes: Anti Additon

101 102

Electrophilic Addition of Bromine to Alkenes: Bromonium Ion Electrophilic Addition of Bromine to Alkenes: Bromonium Ion

103 104
Electrophilic Addition of Bromine to Alkenes: Bromonium Ion Electrophilic Addition of Bromine to Alkenes: Bromonium Ion

105 106

12-6 The Generality of Electrophilic Addition The Generality of Electrophilic Addition

107 108
 Halonium Ion Opening: Regioselective Halonium Ion Opening: Regioselective

109 110

12-7 Oxymercuration–Demecuration Oxymercuration–Demecuration: Mechanism

No carbocation intermediate ó No rearangement! 111 112

Oxymercuration–Demecuration: Mechanism Oxymercuration–Demecuration: Juvenile Hormone Analogs

1000 time more effective; low toxicity; safely degration

113 114

Oxymercuration–Demecuration 12-8 Hydroboration–Oxidation

115 116
 Hydroboration–Oxidation: Mechanism Hydroboration–Oxidation: Oxidation of Alkylboranes

117 118

Hydroboration–Oxidation: Stereospecific and Regioselective 12-9 Diazomethane, Carbenes, and Cyclopropane Synthesis

119 120
Diazomethane, Carbenes, and Cyclopropane Synthesis Diazomethane, Carbenes, and Cyclopropane Synthesis

121 122

12-10 Oxacyclopropane (Epoxide) Synthesis Oxacyclopropane (Epoxide) Synthesis: Mechanism

123 124
 Oxacyclopropane (Epoxide) Synthesis: Mechanism Hydrolysis of Oxacyclopropane: Anti Dihydroxylation

125 126

Hydrolysis of Oxacyclopropane: Anti Dihydroxylation 12-11 Vicinal Syn Dihydroxylation with Osmium Tetroxide

127 128
Vicinal Syn Dihydroxylation with Potassium Permanganate Sharpless Enantioselective Epoxidation

129 130

Sharpless Enantioselective Epoxidation Sharpless Enantioselective Dihydroxylation

131 132
12-12 Oxidative Cleavage: Ozonolysis Oxidative Cleavage: Mechanism

133 134

Oxidative Cleavage: Mechanism 12-13 Radical Additions: Anti-Markovnikov Product Formation

135 136
 Radical Additions: Mechanism 12-14 Dimerization, Oligomerization, and Polimerization

Hydrogen chloride and hydrogen iodide do not give anti-Markovnikov addition

products with alkenes. 137 138

Oligomerization and Polimerization of Alkenes 12-15 Synthesis of Polymers

139 140
 Synthesis of Polymers: Radical Mechanism Synthesis of Polymers: Anionic Mechanism

141 142

Synthesis of Polymers: Ziegler–Natta Catalysis Ziegler–Natta Catalysis: Mechanism

143 144
 Mirozoki–Heck: an Organometallic Reagent Free Cross-Coupling
Ziegler–Natta Catalysis: Mechanism
I I
PdCl2, 10 mol% PdCl2, 10 mol%
AcOK, MeOH nBu N
3

120 °C, 2 hrs 100 °C, 2 hrs

90% yield 75% yield

Mizoroki Bull. Chem. Soc. Jp. 1971, 44, 581 Heck J. Org. Chem. 1972, 37, 2320

Tsutomu Mizoroki succumbed to Richard Fred Heck (born August 15,

pancreatic cancer only nine years after his 1931) is an American chemist noted for
breakthrough discovery of the palladium- the discovery and development of the
catalyzed reaction. Heck reaction. (U. of Delaware)
145 146
http://cenblog.org/newscripts/2010/05/in-search-of-mizoroki-heck/

Mirozoki–Heck: an Organometallic Reagent Free Cross-Coupling Mirozoki–Heck: an Organometallic Reagent Free Cross-Coupling

I I I I
PdCl2, 10 mol% PdCl2, 10 mol% PdCl2, 10 mol% PdCl2, 10 mol%
AcOK, MeOH nBu N AcOK, MeOH nBu N
3 3

120 °C, 2 hrs 100 °C, 2 hrs 120 °C, 2 hrs 100 °C, 2 hrs
90% yield 75% yield 90% yield 75% yield

Mizoroki Bull. Chem. Soc. Jp. 1971, 44, 581 Heck J. Org. Chem. 1972, 37, 2320 Mizoroki Bull. Chem. Soc. Jp. 1971, 44, 581 Heck J. Org. Chem. 1972, 37, 2320

n The good: well functional group tolerance, no organometallic reagent, no need dry
solvent and no need to fully deoxygenate solvents.

n The bad: β–H elimination.

“Unfortunately, Mizoroki died quite young, before he could do much

chemistry with palladium,” Heck says. “Maybe if he’d lived, it might’ve
been called the Mizoroki reaction instead.”
http://cenblog.org/terra-sigillata/2010/10/06/nobel-prize-in-chemistry-2010-to-heck-negishi- How the reaction works?
147 148
and-suzuki-for-pd-catalyzed-cross-couplings/
Mirozoki–Heck: an Organometallic Reagent Free Cross-Coupling The Heck Reactions: Examples

HX RX
LnPd(0)
reductive elimination oxidative addtition
base
X X
LPd H LPd R
(II) (II)
R'

R syn β–H elimination R'

migratory insertion
X H R'
X H R'
LPd
R LPd
(II) H
H (II)
H H
R
C–C bond rotation

How the reaction works? 149 150

The Heck Reactions: In Situ formation of Pd(0) The Heck Reactions: Examples

151 152
 The Heck Reactions: Examples The Heck Reactions: Hydropalladation-Dehydropalladation

153 154

The Heck Reactions: Hydropalladation-Dehydropalladation Mirozoki–Heck Reaction: Synthetic Applications

Danishefsky JACS 1996, 118, 2843

155 156
 Mirozoki–Heck Reaction: Synthetic Applications Mirozoki–Heck Reaction: Synthetic Applications

Me Me Me
BocN Me
Boc
MeO MeO NBoc O
BocN N Me O
BnO O
I O Pd2(dba)3, (o-tol)3P BnO O Me Pd2(dba)3, 20 mol%
O
N N (2-furyl)3P, 20 mol% NR
Me Me NR RN I
TEA,MeCN, RF
OAc OAc DMA, 90 °C NR
MsO O MsO O NBoc
O
O O Me NBoc
Me Me Me R=SEM O
Me
Me
83% yield
Fukuyama JACS 2002, 124, 6552 66% yield
Overman JACS 2001, 123, 9468

157 158

Mirozoki–Heck Coupling: Tandem Reactions Olefin Metathesis

de Meijere, A. Tetrahedron 1996, 52, 11545

159 160
Olefin Metathesis: Mechanism Olefin Metathesis: Mechanism

161 162

Olefin Metathesis: Mechanism Cross Metathesis

163 164
 Ring-Closing Metathesis: Grubb’s Catalyst Ring-Opening Metathesis: Schrock’s Catalyst

165 166

Ring-Opening Metathesis: Natural Product Synthesis Wittig Reaction

167 168
12-16 Ethene: An Important Industrial Feedstock 12-17 Alkenes in Nature: Insect Pheromones

169 170

Chapter Integration Problems

171