Page 14 - Advanced Organic Chemistry Part A - Structure and Mechanisms, 5th ed (2007) - Carey _ Sundberg

xiv 1.4.3. Atoms in Molecules ............................................................................ 63
1.4.4. Comparison and Interpretation of Atomic Charge
Contents
Calculations ......................................................................................... 70
1.4.5. Electrostatic Potential Surfaces........................................................... 73
1.4.6. Relationships between Electron Density and Bond Order................. 76
Topic 1.1. The Origin of the Rotational (Torsional) Barrier in Ethane
and Other Small Molecules................................................................. 78
Topic 1.2. Heteroatom Hyperconjugation (Anomeric Effect)
in Acyclic Molecules........................................................................... 81
Topic 1.3. Bonding in Cyclopropane and Other Small Ring
Compounds.......................................................................................... 85
Topic 1.4. Representation of Electron Density by the Laplacian Function ........ 92
Topic 1.5. Application of Density Functional Theory
to Chemical Properties and Reactivity ............................................... 94
T.1.5.1. DFT Formulation of Chemical Potential,
Electronegativity, Hardness and Softness,
and Covalent and van der Waal Radii................................. 95
T.1.5.2. DFT Formulation of Reactivity—The Fukui Function ....... 97
T.1.5.3. DFT Concepts of Substituent Groups Effects ..................... 100
General References................................................................................................. 106
Problems ................................................................................................................. 106

Chapter 2. Stereochemistry, Conformation, and Stereoselectivity ........ 119

Introduction ............................................................................................................ 119
2.1. Configuration.................................................................................................. 119
2.1.1. Configuration at Double Bonds.......................................................... 119
2.1.2. Configuration of Cyclic Compounds ................................................. 121
2.1.3. Configuration at Tetrahedral Atoms................................................... 122
2.1.4. Molecules with Multiple Stereogenic Centers................................... 126
2.1.5. Other Types of Stereogenic Centers .................................................. 128
2.1.6. The Relationship between Chirality and Symmetry.......................... 131
2.1.7. Configuration at Prochiral Centers..................................................... 133
2.1.8. Resolution—The Separation of Enantiomers..................................... 136
2.2. Conformation.................................................................................................. 142
2.2.1. Conformation of Acyclic Compounds ............................................... 142
2.2.2. Conformations of Cyclohexane Derivatives ...................................... 152
2.2.3. Conformations of Carbocyclic Rings of Other Sizes ........................ 161
2.3. Molecular Mechanics..................................................................................... 167
2.4. Stereoselective and Stereospecific Reactions................................................ 169
2.4.1. Examples of Stereoselective Reactions.............................................. 170
2.4.2. Examples of Stereospecific Reactions ............................................... 182
2.5. Enantioselective Reactions............................................................................. 189
2.5.1. Enantioselective Hydrogenation......................................................... 189
2.5.2. Enantioselective Reduction of Ketones.............................................. 193
2.5.3. Enantioselective Epoxidation of Allylic Alcohols............................. 196
2.5.4. Enantioselective Dihydroxylation of Alkenes.................................... 200
2.6. Double Stereodifferentiation: Reinforcing
and Competing Stereoselectivity ................................................................... 204