CHAPTER 7

Aliphatic Electrophilic Substitution

❖ Bimolecular Mechanisms − SE2 and SEi
The electrophilic substitution in the aliphatic compounds is just similar to the aliphatic nucleophilic
substitution, except for the fact that here an electrophile displaces a functional group rather than an electrophile.
In this section, we will discuss the two major types of electrophilic substitutions; SE2 (substitution electrophilic
bimolecular) and SEi (substitution electrophilic internal) mechanisms.
➢ SE2 (Substitution Electrophilic Bimolecular) Mechanism
The bimolecular electrophilic substitution (SE2) reactions may simply be defined as the chemical
changes where a stronger electrophile displaces a weaker one in an aliphatic substrate.
This mechanism is quite analogous with the SN2 route excepting the mode of attack. In the SN2
mechanism, a stronger nucleophile replaces a weaker one via the backside attack due to its inter-cloud
repulsion with the leaving group; however, in the SE2 route, the attacking electrophile may come from the
front, as well as from the backside because it is only using is vacant orbital towards substates causing little to
no repulsion. So, the SE2 mechanism can be divided into SE2-front and SE2-back based upon the front and
back attacks, respectively.
Illustrative reaction: The general reaction showing both types of electrophilic attacks (with their
corresponding products), is shown below.

Mechanism involved: The proposed mechanism for the reaction given above says that the two electrons of
the carbon-electrophile bond reside in the central orbital. Ingold proposed that the electronic distribution
responsible for different stereochemistry of products is a function of bond-extension’s magnitude and the
extent of bond ionicity of the transition state.

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 CHAPTER 7: Aliphatic Electrophilic Substitution 303

It is obvious that the transition state needs to have high ionicity and good bond extension potential for SE2-
back reactions so that the carbon’s orbital is sufficiently spread on both ends, resulting in the inverted
configuration in the case of a chiral substrate. On the other hand, if there is a very little bond extension and
low ionicity in the transition state, the electron-pair of the original bond pretty much retains its position and
gives rise to the retention of the configuration, and we get SE2-front case.

Where E+ is the attacking electrophile whereas L+ is the leaving group. Furthermore, it is also worthy to note
that organometallic compounds have exceptional susceptibility towards electrophilic substitution.
Salient Features: The main features of the mechanism involved in electrophilic substitution bimolecular or
SE2 type reactions are given below.
i) SE2 reactions follow second-order kinetics with the rate law

𝑅𝑎𝑡𝑒 = 𝑘[𝑅𝑋][𝐸]

Where k is the rate constant. The symbol [𝑅𝑋] and [𝐸] represent the molar concentration of the substrate and
attacking electrophile, respectively.
ii) If the substrate is chiral, then the SE2 mechanism can lead to the inversion, as well as, retention of the
configuration; depending upon the mode of attack (front or back).
iii) The rate of the substitution becomes independent of the concentration of the attacking electrophile if its
concentration is extremely high in comparison to the substrate.
iv) Stereochemical studies can be employed to differentiate between SE 2-front and SE2-back.
v) The SE2 reactions are favored by the more polar C−L bond.

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 304 A Textbook of Organic Chemistry – Volume I

➢ SEi (Substitution Electrophilic Internal) Mechanism

The internal electrophilic substitution (SEi) reactions may simply be defined as the chemical changes
where a stronger electrophile displaces a weaker one in an aliphatic substrate by assisting its departure.
This mechanism is also very analogous with the SN2 route excepting the mode of attack. In the SN 2
mechanism, a stronger nucleophile replaces a weaker one via the backside attack due to its inter-cloud
repulsion with the leaving group; however, in the SE i route, the attacking electrophile comes from the front
and assists the departure of leaving group by forming a bond with it.
Illustrative reaction: The general reaction showing this type of electrophilic attack (with the corresponding
product) is shown below.

Mechanism involved: The proposed mechanism for the reaction given above says that the two electrons of
the carbon-electrophile bond reside in the central orbital. It is observed that if there is a very little bond
extension and low ionicity in the transition state, the electron-pair of the original bond pretty much retains its
position and gives rise to the retention of the configuration, and we get SEi case (like SE2-front).

Salient Features: The main features of the mechanism involved in electrophilic substitution internal or SEi
type reactions are given below.
i) SEi reactions follow second-order kinetics with the rate law

𝑅𝑎𝑡𝑒 = 𝑘[𝑅𝑋][𝐸𝑍]

Where k is the rate constant. The symbol [𝑅𝑋] and [𝐸𝑍] represent the molar concentration of the substrate and
attacking electrophile, respectively.
ii) Like SE2-front, SEi reactions result in the retention of the configuration.
iii) The SE2 reactions are favored by the more polar C−L bond.

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CHAPTER 7: Aliphatic Electrophilic Substitution 305

❖ The SE1 Mechanism

The unimolecular electrophilic substitution (SE1) reactions may simply be defined as the chemical
change in which a stronger electrophile displaces a weaker one in an aliphatic substrate via the formation of
a carbanion.
This mechanism is quite analogous with the SN 1 route excepting the nature of intermediate. In the
SN1 mechanism, a stronger nucleophile replaces a weaker one via the formation of a carbocation intermediate;
however, in the SE1 route, before the attacking electrophile attack, the intermediate formed after the
dissociation of electrofuge is a carbanion.
Illustrative reaction: The general reaction showing this type of electrophilic attack (with its corresponding
product) is shown below.

Mechanism involved: The proposed mechanism for the reaction given above involves a three-step route which
must be discussed before we give the salient features of the same.
i) Heterolysis in substrate: This is the slowest, and therefore, is the rate-determining step that gives rise to a
carbanion.

ii) Electrophilic attack: This is a very fast step and involves the combination of attacking electrophile with the
carbanion produced in the previous step.

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 306 A Textbook of Organic Chemistry – Volume I

The stereochemistry of SE1 reactions is quite complicated to rationalize because of the configuration
of intermediatory carbanions obtained via the first step of heterolysis. Generally, we consider carbanions planar
(sp2 hybridization) or pyramidal (sp3 hybridization), or an in-between configuration. As far as the energy is
concerned, pyramidal geometry is more advantageous because lone pair will stay in sp3 hybridized orbital.
Furthermore, a pyramidal carbanion can retain its structure in the course of substitution to result in the retention
of the final configuration. However, it does not always go this way because a pyramidal carbanion has been
shown to results in racemization due to ‘pyramidal inversion’; amines and R 3C− carbanions are typical
examples.

Figure 1. The pyramidal inversion of carbanion.

On the other hand, if the carbanion is of trigonal planar geometry, the electrophile can attack from both sides
to give rise to racemized yield. So, we can conclude that racemization is the characteristic feature of the SE1
route. However, it is quite tedious to determine how the racemization actually occurred; via pyramidal
inversion or planar carbanions.
Salient Features: The main features of the mechanism involved in electrophilic substitution unimolecular or
SE1 type reactions are given below.
i) SE2 reactions follow first-order kinetics with the rate law

𝑅𝑎𝑡𝑒 = 𝑘[𝑅𝑋]

Where k is the rate constant. The symbol [𝑅𝑋] represents the molar concentration of the substrate.
ii) If the substrate is chiral, then this always leads to the racemization of the final product.
iii) Unlike SN1-type, SE1 reaction can also occur at bridgehead carbon because the intermediate (carbanion in
this case) need not to be planar.
iv) The rate of the substitution increases as the steric bulk around the carbon center decreases.
v) The SE2 reactions are favored by the more polar C−L bond.

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CHAPTER 7: Aliphatic Electrophilic Substitution 307

❖ Electrophilic Substitution Accompanied by Double Bond Shifts

If the substrate in electrophilic substitution is allylic in nature, the final product may undergo
rearrangement, which is quite similar to the allylic rearrangements in nucleophilic substitutions. There are two
main routes for this behavior to occur; one is analogous to the SE 1 pathway (leaving group is detached first)
giving a resonance-stabilized allylic carbanion which attacks the electrophile E, the second one involves the
initial attack on E by the π-bond to yield a carbocation which then which loses X forming new alkene unit.
➢ Base-catalyzed Double Bond Migration
The first pathway is the base-catalyzed double bond migration, where an equilibrium mixture of
isomers is obtained with stable configuration as the major product. The reaction occurs in two steps, in which
the step is the abstraction of a proton by the base to yield a resonance stabilized carbanion, which in turn, is
attacked by electrophile (proton in this case) to give rise to a more stable species. The typical reaction
portraying mechanism is given below.

It is also worthy to note that terminal and non-conjugated alkenes can easily be converted into internal and
conjugated olefins using this route, proving its significance in synthetic organic chemistry.
➢ Acid-catalyzed Double Bond Migration
The second pathway is the acid-catalyzed double bond migration, where an equilibrium mixture of
isomers is obtained with a stable configuration as the major product. The reaction initiates with the attack of
E on the π-bond to yield a carbocation which then loses L forming a new alkene unit. The typical reaction
portraying mechanism is given below.

Just like base-catalyzed double bond migration, this route can also be used to convert terminal and non-
conjugated alkenes into internal and conjugated olefins.

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308 A Textbook of Organic Chemistry – Volume I

❖ Effect of Substrates, Leaving Group and the Solvent Polarity on the

Reactivity
The reactivity of aliphatic electrophilic substitution reactions is affected by many factors that can be
better understood via experimental data and theoretical treatment combined. In this section, we will discuss
some major factors that greatly influence the electrophilic substitution’s rate in aliphatic compounds like
substrate structure, leaving group and reaction medium.
➢ Effect of Substrate Structure
The electron-donating groups of the substrate decrease the rate of SE 1 reactions whereas electron-
withdrawing groups show an opposite trend. This declining rate in the SE 1 pathway with electron-donating
groups is quite normal for a reaction-type where the proton’s dissociation is the rate-determining step (like in
the case of acidic character). Jensen and Davis proved that the reactivity of alkyl groups is similar in SE 2-back
as that for the SN2 pathway, which can be attributed to the backside attack and steric hindrance, simultaneously.

Furthermore, it has also been observed that the rate of front-mode electrophilic substitution in aliphatic
compounds increases as the branching in the substrate increases increased, which can be attributed to the
electron-releasing effect of the alkyl groups that makes the electron-deficient transition state more stable.
However, it is also worthy to note that β-branching will reduce the substitution rate in SE2-front because of the
steric hindrance.
➢ Effect of Leaving Group
The ease of electrofuge’s detachment in both types (SE1 and SE2) increases with the increasing
polarity of the C−X bond. Nevertheless, if the leaving group is metallic in nature and metal has a valence
greater than one, then any group attached to the metal center will affect its electrofugal ability. For instance,
consider the case of Me3C−Hg−W (organomercurials) where the rate of reaction has decreased. The reason
lies in the fact that although Hg and W have less electronegativity than carbon (which is why the C−Hg bond
is polar), the C−Hg bond becomes less polar due to the higher electronegativity W than Hg. In other words,
carbon will have a lower negative charge in the C−Hg bond when W is attached to Hg because tungsten will
support Hg to hold the shared pair more firmly. Therefore, −HgMe will be a better leaving group than −HgCl.

Furthermore, it is also worthy to note that carbon-based leaving groups support the SE1 mechanism, whereas
SE2 or SEi mechanisms are favored by metal-based leaving groups.

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 CHAPTER 7: Aliphatic Electrophilic Substitution 309

➢ Effect of Solvent Polarity

Just like the case of aliphatic nucleophilic substitution reactions, the raise in solvent polarity boosts
the chances of the SE1 pathway by supporting the ionization because of the better solvation of carbanions.
However, if SE2 and SE1 reactions are competing with each other in parallel propagation, then less polar
solvents favor the SE2 pathway and polar solvents favor the SE 1 mechanism. Finally, If the nucleophilic
character of the solvent is very small, the electrophile with properly placed assisting functionality might
support the reaction; and therefore, motivating the reaction towards the SE i pathway; otherwise, solvent
polarity has little to no effect upon SNi reactions.

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310 A Textbook of Organic Chemistry – Volume I

❖ Problems
Q 1. Define electrophilic substitution reactions.
Q 2. What is the fundamental difference between SE 2 and SEi mechanisms?
Q 3. Discuss the step-to-step mechanism of SE1 reactions.
Q 4. How can electrophilic substitution occur via double bond shift?
Q 5. Discuss the effect of substrate structure and leaving group on the reactivity of electrophilic substitution
in aliphatic compounds.
Q 6. How does the nature of nucleophiles affect the rate of aliphatic electrophilic substitution?
Q 7. Write down a short note on the solvent polarity’s effect on electrophilic substitution reactions in aliphatic
systems.

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CHAPTER 7: Aliphatic Electrophilic Substitution 311

❖ Bibliography
1. M. B. Smith, March’s Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, John Wiley &
Sons, Inc., New Jersey, USA, 2013.
2. D. Klein, Organic Chemistry, John Wiley & Sons, Inc., New Jersey, USA, 2015.
3. C. A. Coulson, B. O'Leary, R. B. Mallion, Hückel Theory for Organic Chemists, Academic Press,
Massachusetts, USA, 1978.
4. M.S. Singh, Reactive Intermediates in Organic Chemistry, John Wiley & Sons, Inc., New Jersey, USA,
2014.
5. H. Zimmerman, Quantum Mechanics for Organic Chemists, Academic Press, New York, USA, 1975.
6. J. Clayden, N. Greeves, S. Warren, Organic Chemistry, Oxford University Press, Oxford, UK, 2012.
7. R. L. Madan, Organic Chemistry, Tata McGraw Hill, New Delhi India, 2013.

Copyright © Mandeep Dalal

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Table of Contents
CHAPTER 1 ................................................................................................................................................. 11
Nature of Bonding in Organic Molecules ............................................................................................... 11
❖ Delocalized Chemical Bonding ...................................................................................................... 11
❖ Conjugation .................................................................................................................................... 14
❖ Cross Conjugation .......................................................................................................................... 16
❖ Resonance....................................................................................................................................... 18
❖ Hyperconjugation ........................................................................................................................... 27
❖ Tautomerism ................................................................................................................................... 31
❖ Aromaticity in Benzenoid and Nonbenzenoid Compounds ............................................................ 33
❖ Alternant and Non-Alternant Hydrocarbons ................................................................................... 35
❖ Huckel’s Rule: Energy Level of π-Molecular Orbitals ................................................................... 3 7
❖ Annulenes ....................................................................................................................................... 44
❖ Antiaromaticity ............................................................................................................................... 46
❖ Homoaromaticity ............................................................................................................................ 48
❖ PMO Approach ............................................................................................................................... 50
❖ Bonds Weaker Than Covalent ........................................................................................................ 58
❖ Addition Compounds: Crown Ether Complexes and Cryptands, Inclusion Compounds,
Cyclodextrins ................................................................................................................................. 65
❖ Catenanes and Rotaxanes ............................................................................................................... 75
❖ Problems ......................................................................................................................................... 79
❖ Bibliography ................................................................................................................................... 80
CHAPTER 2 ................................................................................................................................................. 81
Stereochemistry ........................................................................................................................................ 81
❖ Chirality .......................................................................................................................................... 81
❖ Elements of Symmetry ................................................................................................................... 86
❖ Molecules with More Than One Chiral Centre: Diastereomerism .................................................. 90
❖ Determination of Relative and Absolute Configuration (Octant Rule Excluded) with Special
Reference to Lactic Acid, Alanine & Mandelic Acid ..................................................................... 92
❖ Methods of Resolution.................................................................................................................. 102
❖ Optical Purity ............................................................................................................................... 104
❖ Prochirality ................................................................................................................................... 105
❖ Enantiotopic and Diastereotopic Atoms, Groups and Faces ......................................................... 107
❖ Asymmetric Synthesis: Cram’s Rule and Its Modifications, Prelog’s Rule .................................. 113
❖ Conformational Analysis of Cycloalkanes (Upto Six Membered Rings) ...................................... 116
❖ Decalins ........................................................................................................................................ 122
❖ Conformations of Sugars .............................................................................................................. 126
❖ Optical Activity in Absence of Chiral Carbon (Biphenyls, Allenes and Spiranes) ....................... 132
❖ Chirality Due to Helical Shape ..................................................................................................... 137
❖ Geometrical Isomerism in Alkenes and Oximes ........................................................................... 140
❖ Methods of Determining the Configuration .................................................................................. 146
 ❖ Problems ....................................................................................................................................... 151
❖ Bibliography ................................................................................................................................. 152
CHAPTER 3 ............................................................................................................................................... 153
Reaction Mechanism: Structure and Reactivity .................................................................................. 153
❖ Types of Mechanisms ................................................................................................................... 153
❖ Types of Reactions ....................................................................................................................... 156
❖ Thermodynamic and Kinetic Requirements .................................................................................. 159
❖ Kinetic and Thermodynamic Control ........................................................................................... 161
❖ Hammond’s Postulate ................................................................................................................... 163
❖ Curtin-Hammett Principle ............................................................................................................ 164
❖ Potential Energy Diagrams: Transition States and Intermediates ................................................. 166
❖ Methods of Determining Mechanisms .......................................................................................... 168
❖ Isotope Effects .............................................................................................................................. 172
❖ Hard and Soft Acids and Bases ..................................................................................................... 174
❖ Generation, Structure, Stability and Reactivity of Carbocations, Carbanions, Free Radicals, Carbenes
and Nitrenes................................................................................................................................. 176
❖ Effect of Structure on Reactivity .................................................................................................. 200
❖ The Hammett Equation and Linear Free Energy Relationship ...................................................... 203
❖ Substituent and Reaction Constants .............................................................................................. 209
❖ Taft Equation ................................................................................................................................ 215
❖ Problems ....................................................................................................................................... 219
❖ Bibliography ................................................................................................................................. 220
CHAPTER 4 ............................................................................................................................................... 221
Carbohydrates ........................................................................................................................................ 221
❖ Types of Naturally Occurring Sugars ........................................................................................... 221
❖ Deoxy Sugars ............................................................................................................................... 227
❖ Amino Sugars ............................................................................................................................... 229
❖ Branch Chain Sugars .................................................................................................................... 230
❖ General Methods of Determination of Structure and Ring Size of Sugars with Particular Reference
to Maltose, Lactose, Sucrose, Starch and Cellulose ...................................................................... 231
❖ Problems ....................................................................................................................................... 239
❖ Bibliography ................................................................................................................................. 240
CHAPTER 5 ............................................................................................................................................... 241
Natural and Synthetic Dyes ................................................................................................................... 241
❖ Various Classes of Synthetic Dyes Including Heterocyclic Dyes ................................................. 241
❖ Interaction Between Dyes and Fibers ........................................................................................... 245
❖ Structure Elucidation of Indigo and Alizarin ................................................................................ 247
❖ Problems ....................................................................................................................................... 252
❖ Bibliography ................................................................................................................................. 253
CHAPTER 6 ............................................................................................................................................... 254
Aliphatic Nucleophilic Substitution ...................................................................................................... 254
❖ The SN2, SN1, Mixed SN1 and SN2, SNi, SN1′, SN2′, SNi′ and SET Mechanisms ......................... 254
 The Neighbouring Group Mechanisms ......................................................................................... 263
❖
Neighbouring Group Participation by π and σ Bonds . .................................................................. 2 65
❖
Anchimeric Assistance ................................................................................................................. 269
❖
Classical and Nonclassical Carbocations ...................................................................................... 272
❖
Phenonium Ions ............................................................................................................................ 283
❖
Common Carbocation Rearrangements ........................................................................................ 284
❖
Applications of NMR Spectroscopy in the Detection of Carbocations ......................................... 286
❖
Reactivity – Effects of Substrate Structure, Attacking Nucleophile, Leaving Group and Reaction
❖
Medium ........................................................................................................................................ 288
❖ Ambident Nucleophiles and Regioselectivity ............................................................................... 294
❖ Phase Transfer Catalysis ............................................................................................................... 297
❖ Problems ....................................................................................................................................... 300
❖ Bibliography ................................................................................................................................. 301
CHAPTER 7 ............................................................................................................................................... 302
Aliphatic Electrophilic Substitution ...................................................................................................... 302
❖ Bimolecular Mechanisms − SE2 and SEi ...................................................................................... 3 02
❖ The SE1 Mechanism ..................................................................................................................... 305
❖ Electrophilic Substitution Accompanied by Double Bond Shifts ................................................. 307
❖ Effect of Substrates, Leaving Group and the Solvent Polarity on the Reactivity .......................... 308
❖ Problems ....................................................................................................................................... 310
❖ Bibliography ................................................................................................................................. 311
CHAPTER 8 ............................................................................................................................................... 312
Aromatic Electrophilic Substitution ..................................................................................................... 312
❖ The Arenium Ion Mechanism ....................................................................................................... 312
❖ Orientation and Reactivity ............................................................................................................ 314
❖ Energy Profile Diagrams .............................................................................................................. 316
❖ The Ortho/Para Ratio .................................................................................................................... 317
❖ ipso-Attack ................................................................................................................................... 319
❖ Orientation in Other Ring Systems ............................................................................................... 320
❖ Quantitative Treatment of Reactivity in Substrates and Electrophiles .......................................... 321
❖ Diazonium Coupling..................................................................................................................... 325
❖ Vilsmeier Reaction ....................................................................................................................... 326
❖ Gattermann-Koch Reaction .......................................................................................................... 327
❖ Problems ....................................................................................................................................... 329
❖ Bibliography ................................................................................................................................. 330
CHAPTER 9 ............................................................................................................................................... 331
Aromatic Nucleophilic Substitution ...................................................................................................... 331
❖ The ArSN1, ArSN2, Benzyne and SRN1 Mechanisms.................................................................... 331
❖ Reactivity – Effect of Substrate Structure, Leaving Group and Attacking Nucleophile................ 336
❖ The von Richter, Sommelet-Hauser, and Smiles Rearrangements ................................................ 339
❖ Problems ....................................................................................................................................... 343
❖ Bibliography ................................................................................................................................. 344
CHAPTER 10 ............................................................................................................................................. 345
Elimination Reactions ............................................................................................................................ 345
❖ The E2, E1 and E1CB Mechanisms ................................................................................................ 345
❖ Orientation of the Double Bond.................................................................................................... 348
❖ Reactivity – Effects of Substrate Structures, Attacking Base, the Leaving Group and The Medium
....................................................................................................................................................352
❖ Mechanism and Orientation in Pyrolytic Elimination ................................................................... 355
❖ Problems ....................................................................................................................................... 358
❖ Bibliography ................................................................................................................................. 359
CHAPTER 11 ............................................................................................................................................. 360
Addition to Carbon-Carbon Multiple Bonds ....................................................................................... 360
❖ Mechanistic and Stereochemical Aspects of Addition Reactions Involving Electrophiles,
Nucleophiles and Free Radicals .................................................................................................... 360
❖ Regio- and Chemoselectivity: Orientation and Reactivity ............................................................ 370
❖ Addition to Cyclopropane Ring .................................................................................................... 374
❖ Hydrogenation of Double and Triple Bonds ................................................................................. 375
❖ Hydrogenation of Aromatic Rings ................................................................................................ 377
❖ Hydroboration .............................................................................................................................. 378
❖ Michael Reaction .......................................................................................................................... 379
❖ Sharpless Asymmetric Epoxidation .............................................................................................. 380
❖ Problems ....................................................................................................................................... 382
❖ Bibliography ................................................................................................................................. 383
CHAPTER 12 ............................................................................................................................................. 384
Addition to Carbon-Hetero Multiple Bonds ......................................................................................... 384
❖ Mechanism of Metal Hydride Reduction of Saturated and Unsaturated Carbonyl Compounds, Acids,
Esters and Nitriles ......................................................................................................................... 384
❖ Addition of Grignard Reagents, Organozinc and Organolithium Reagents to Carbonyl and
Unsaturated Carbonyl Compounds ............................................................................................... 400
❖ Wittig Reaction ............................................................................................................................. 406
❖ Mechanism of Condensation Reactions Involving Enolates: Aldol, Knoevenagel, Claisen, Mannich,
Benzoin, Perkin and Stobbe Reactions .......................................................................................... 411
❖ Hydrolysis of Esters and Amides .................................................................................................. 433
❖ Ammonolysis of Esters ................................................................................................................. 437
❖ Problems ....................................................................................................................................... 439
❖ Bibliography ................................................................................................................................. 440
INDEX......................................................................................................................................................... 441