Page 15 - Advanced Organic Chemistry Part A - Structure and Mechanisms, 5th ed (2007) - Carey _ Sundberg

Topic 2.1. Analysis and Separation of Enantiomeric Mixtures........................... 208 xv
T.2.1.1. Chiral Shift Reagents and Chiral
Contents
Solvating Agents................................................................... 208
T.2.1.2. Separation of Enantiomers ................................................... 211
Topic 2.2. Enzymatic Resolution and Desymmetrization.................................... 215
T.2.2.1. Lipases and Esterases........................................................... 216
T.2.2.2. Proteases and Acylases ........................................................ 222
T.2.2.3. Epoxide Hydrolases.............................................................. 224
Topic 2.3. The Anomeric Effect in Cyclic Compounds ...................................... 227
Topic 2.4. Polar Substituent Effects in Reduction
of Carbonyl Compounds ..................................................................... 234
General References................................................................................................. 239
Problems ................................................................................................................. 240

Chapter 3. Structural Effects on Stability and Reactivity................ 253

Introduction............................................................................................................. 253
3.1. Thermodynamic Stability............................................................................... 254
3.1.1. Relationship between Structure and Thermodynamic
Stability for Hydrocarbons ................................................................. 256
3.1.2. Calculation of Enthalpy of Formation and
Enthalpy of Reaction .......................................................................... 257
3.2. Chemical Kinetics .......................................................................................... 270
3.2.1. Fundamental Principles of Chemical Kinetics................................... 270
3.2.2. Representation of Potential Energy
Changes in Reactions.......................................................................... 273
3.2.3. Reaction Rate Expressions ................................................................. 280
3.2.4. Examples of Rate Expressions ........................................................... 283
3.3. General Relationships between Thermodynamic Stability
and Reaction Rates......................................................................................... 285
3.3.1. Kinetic versus Thermodynamic Control
of Product Composition...................................................................... 285
3.3.2. Correlations between Thermodynamic and Kinetic Aspects
of Reactions ........................................................................................ 287
3.3.3. Curtin-Hammett Principle................................................................... 296
3.4. Electronic Substituent Effects on Reaction Intermediates ............................ 297
3.4.1. Carbocations........................................................................................ 300
3.4.2. Carbanions .......................................................................................... 307
3.4.3. Radical Intermediates ......................................................................... 311
3.4.4. Carbonyl Addition Intermediates ....................................................... 319
3.5. Kinetic Isotope Effects................................................................................... 332
3.6. Linear Free-Energy Relationships for Substituent Effects............................ 335
3.6.1. Numerical Expression of Linear Free-Energy
Relationships....................................................................................... 335
3.6.2. Application of Linear Free-Energy Relationships
to Characterization of Reaction Mechanisms .................................... 342
3.7. Catalysis ......................................................................................................... 345
3.7.1. Catalysis by Acids and Bases............................................................. 345
3.7.2. Lewis Acid Catalysis.......................................................................... 354