CHAPTER 1 BOND-LINE DRAWINGS 1 1.1 How to Read Bond-Line Drawings 1 1.2 How to Draw Bond-Line Drawings 5 1.3 Mistakes to Avoid 7 1.4 More Exercises 7 1.5 Identifying Formal Charges 10 1.6 Finding Lone Pairs That Are Not Drawn 14 CHAPTER 2 RESONANCE 20 2.1 What Is Resonance? 20 2.2 Curved Arrows: The Tools for Drawing Resonance Structures 21 2.3 The Two Commandments 24 2.4 Drawing Good Arrows 27 2.5 Formal Charges in Resonance Structures 29 2.6 Drawing Resonance Structures Step by Step 33 2.7 Drawing Resonance Structures By Recognizing Patterns 38 A Lone Pair Next to a Pi Bond 38 A Lone Pair Next to a Positive Charge 41 A Pi Bond Next to a Positive Charge 43 A Pi Bond Between Two Atoms, Where One of Those Atoms Is Electronegative (N, O, etc.) 44 Pi Bonds Going All the Way Around a Ring 45 2.8 Assessing the Relative Importance of Resonance Structures 47 CHAPTER 3 ACID BASE REACTIONS 53 3.1 Factor 1 What Atom Is the Charge on? 54 3.2 Factor 2 Resonance 57 3.3 Factor 3 Induction 61 3.4 Factor 4 Orbitals 64 3.5 Ranking the Four Factors 65 3.6 Quantitative Measurement (pKa values) 69 3.7 Predicting the Position of Equilibrium 70 3.8 Showing a Mechanism 71 CHAPTER 4 GEOMETRY 74 4.1 Orbitals and Hybridization States 74 4.2 Geometry 78 4.3 Lone Pairs 81 CHAPTER 5 NOMENCLATURE 83 5.1 Functional Group 84 5.2 Unsaturation 86 5.3 Naming the Parent Chain 88 5.4 Naming Substituents 90 5.5 Stereoisomerism 94 5.6 Numbering 97 5.7 Common Names 102 5.8 Going from a Name to a Structure 103 CHAPTER 6 CONFORMATIONS 104 6.1 How to Draw a Newman Projection 105 6.2 Ranking the Stability of Newman Projections 109 6.3 Drawing Chair Conformations 113 6.4 Placing Groups on the Chair 116 6.5 Ring Flipping 121 6.6 Comparing the Stability of Chairs 127 6.7 Don t Be Confused by the Nomenclature 131 CHAPTER 7 CONFIGURATIONS 132 7.1 Locating Stereocenters 133 7.2 Determining the Configuration of a Stereocenter 136 7.3 Nomenclature 144 7.4 Drawing Enantiomers 149 7.5 Diastereomers 154 7.6 Meso Compounds 155 7.7 Drawing Fischer Projections 158 7.8 Optical Activity 163 CHAPTER 8 MECHANISMS 165 8.1 Curved Arrows 166 8.2 Arrow Pushing 171 8.3 Drawing Intermediates 173 8.4 Nucleophiles and Electrophiles 176 8.5 Bases Versus Nucleophiles 177 8.6 The Regiochemistry Is Contained Within the Mechanism 180 8.7 The Stereochemistry Is Contained Within the Mechanism 183 8.8 A List of Mechanisms 188 CHAPTER 9 SUBSTITUTION REACTIONS 209 9.1 The Mechanisms 209 9.2 Factor 1 The Electrophile (Substrate) 212 9.3 Factor 2 The Nucleophile 215 9.4 Factor 3 The Leaving Group 217 9.5 Factor 4 The Solvent 220 9.6 Using All Four Factors 223 9.7 Substitution Reactions Teach Us Some Important Lessons 224 CHAPTER 10 ELIMINATION REACTIONS 226 10.1 The E2 Mechanism 226 10.2 The Regiochemical Outcome of an E2 Reaction 227 10.3 The Stereochemical Outcome of an E2 Reaction 229 10.4 The E1 Mechanism 232 10.5 The Regiochemical Outcome of an E1 Reaction 233 10.6 The Stereochemical Outcome of an E1 Reaction 234 10.7 Substitution vs. Elimination 234 10.8 Determining the Function of the Reagent 235 10.9 Identifying the Mechanism(s) 238 10.10 Predicting the Products 241 CHAPTER 11 ADDITION REACTIONS 245 11.1 Terminology Describing Regiochemistry 245 11.2 Terminology Describing Stereochemistry 247 11.3 Adding H and H 256 11.4 Adding H and X, Markovnikov 259 11.5 Adding H and Br, Anti-Markovnikov 266 11.6 Adding H and OH, Markovnikov 271 11.7 Adding H and OH, Anti-Markovnikov 275 11.8 Synthesis Techniques 279 11.9 Adding Br and Br; Adding Br and OH 287 11.10 Adding OH and OH, Anti 293 11.11 Adding OH and OH, Syn 296 11.12 Oxidative Cleavage of an Alkene 298 CHAPTER 12 ALCOHOLS 302 12.1 Naming and Designating Alcohols 302 12.2 Predicting Solubility of Alcohols 303 12.3 Predicting Relative Acidity of Alcohols 306 12.4 Preparing Alcohols: A Review 309 12.5 Preparing Alcohols via Reduction 310 12.6 Preparing Alcohols via Grignard Reactions 317 12.7 Summary of Methods for Preparing Alcohols 322 12.8 Reactions of Alcohols: Substitution and Elimination 323 12.9 Reactions of Alcohols: Oxidation 327 12.10 Converting an Alcohol into an Ether 329 CHAPTER 13 SYNTHESIS 332 13.1 One-step Syntheses 333 13.2 Multistep Syntheses 345 13.3 Retrosynthetic Analysis 346 13.4 Creating Your Own Problems 347 Answer Key 349 Index 375
