Structure and Reactivity in Organic Chemistry Book

Preface     xi
Bonding     1
Atomic structure     1
The chemical bond     1
The periodic table     1
Valence electrons     3
Lewis structures     3
Conventions for drawing structures     5
Atomic orbital theory     6
Molecular orbital theory     7
Covalent bonding     10
Bonding in hydrocarbons     11
Bonding in compounds containing heteroatoms     12
Bonding in common functional groups     12
Electronic effects     14
Steric effects     18
Stereoelectronic effects     18
Double bond equivalents     20
Structure     21
Configuration     21
Geometrical isomerism     22
Optical isomerism     23
Representations of stereoisomers     25
Molecules with one stereogenic centre     27
Molecules with more than one stereogenic centre     27
Molecules with more than one stereogenic centre which are not optically active     28
Optically active molecules without stereogenic centres: molecular asymmetry     29
Asymmetric heteroatoms     30
Conformation     31
Representation of conformers     31
Open-chain compounds     31
Ring compounds     33
Summary of stereochemical relationships     39
Naturally occurring chiral compounds     39
Asymmetric synthesis     41
Enantioselective synthesis     41
Diastereoselective synthesis     43
Methods for the determination of enantiomeric purity     43
Reactivity     47
Thermodynamics     47
Gibbs free energy     47
Enthalpy     48
Entropy     50
Chemical equilibrium     52
Kinetics     54
Rates of reaction     54
Reactions with competing steps     57
Overcoming activation energy barriers     58
Reaction mechanism     60
What is reactivity?     60
Lewis acids and bases: 'philicity'     60
Polarisability effects: Hard-Soft Acid-Base theory     61
Curly ('curved') arrows     63
Classes of reaction mechanism     66
Polar mechanisms     66
Radical mechanisms     67
Pericyclic mechanisms     67
Ligand coupling reaction mechanisms     67
Principle of microscopic reversibility     68
Selectivity of reactions     69
Solvents in organic chemistry     71
Redox reactions in organic chemistry     72
Intermediates     77
Carbocations     77
Structure     77
Factors stabilising carbocations     77
Generation of carbocations     81
Rearrangements of carbocations     82
Carbanions     82
Structure     82
Carbanions derived from simple alkanes     84
Factors stabilising carbanions     85
Carbanions with covalent character     88
Grignard reagents (RMgX)     88
Organolithium reagents (RLi)     89
Organocadmium reagents     89
Radicals     90
Structure     90
Factors stabilising radicals     90
Generation of radicals     92
Carbenes     94
Stability and structure     94
Generation of carbenes     95
Benzynes     96
Stability and structure     96
Generation of benzynes     97
Ketenes      98
Stability and structure     98
Generation of ketenes     98
Acidity and Basicity     99
Lowry-Bronsted Acid-Base theory     99
Organic acidity     100
Organic acids     100
Organic basicity     111
Organic bases     112
Nucleophilic Substitution     117
The S[subscript N]1 reaction     117
Factors affecting the S[subscript N]1 reaction     118
The S[subscript N]2 reaction     123
Factors enhancing the S[subscript N]2 reaction     124
Synthetic applications of nucleophilic substitution reactions     128
Protecting-group chemistry     128
Stereocontrolled alkylation reactions     131
Addition Reactions     139
Electrophilic addition reactions     139
Addition of halogens     139
Addition of hydrogen halides     141
Addition of hydrogen halides to conjugated dienes     143
Addition of diborane (hydroboration)     143
Addition of hydrogen     147
Addition of oxygen     148
Addition of carbon     153
Nucleophilic addition reactions     153
Irreversible nucleophilic addition      154
Irreversible nucleophilic conjugate addition     159
Reversible nucleophilic addition     160
Additions to electron-deficient alkenes     165
Additions of ketenes     165
Synthetic applications     166
Elimination Reactions     169
Eliminations     169
E[subscript 1] reactions     169
E[subscript 1]CB reactions     169
E[subscript 2] reactions     170
Eliminations leading to isomeric products     173
Competition between substitution and elimination     175
The leaving group     176
Oxidation processes     178
[alpha]-Eliminations leading to carbenes and nitrenes     181
Eliminations of phosphorus     182
Eliminations of sulfur and selenium     182
Eliminations in protecting-group chemistry     184
Aromatic Substitution     189
Aromaticity     189
Benzene     189
Heteroaromatics     189
Reactions     191
Acidity and basicity     191
Electrophilic aromatic substitution     191
Orientation effects in electrophilic aromatic substitution (S[subscript E]Ar)      202
o-Lithiation     205
Nucleophilic aromatic substitution     206
Arene chromium tricarbonyl complexes     211
Sequential Addition and Elimination Reactions     213
Addition-elimination reactions     213
Addition of hydride     220
Addition of heteroatom nucleophiles     221
Addition of carbon nucleophiles     222
Addition of phosphorus nucleophiles     225
Addition-elimination reactions in conjugated systems     230
Addition-elimination reactions in heterocyclic systems     230
Addition-elimination reactions in ring-closing metathesis     231
Addition-elimination reactions in deprotections     234
Radical Reactions     237
Generation     237
Reactions     237
Termination     237
Propagation     238
Substitution     239
Addition reactions     242
Fragmentation     249
Rearrangement     250
Synthetic utility     255
Ligand Coupling Reactions     263
Palladium-mediated couplings     263
Palladium-mediated coupling processes     264
Heck coupling      271
Allylic coupling processes     273
Ligand coupling processes mediated by other elements     275
Copper     276
Magnesium     277
Lead     279
Pericyclic Reactions     283
Molecular orbitals and the FMO approach     283
Pericyclic reactions     284
Electrocyclic reactions     285
Cycloaddition reactions     287
Sigmatropic reactions     293
Synthetic applications of pericyclic reactions     296
Index     303