Chapter 1 Bond-Line Drawings 1 1.1 How to Read Bond-Line Drawings 1 1.2 How to Draw Bond-Line Drawings 4 1.3 Mistakes to Avoid 6 1.4 More Exercises 6 1.5 Identifying Formal Charges 8 1.6 Finding Lone Pairs that are Not Drawn 11 Chapter 2 Resonance 15 2.1 What is Resonance? 15 2.2 Curved Arrows: The Tools for Drawing Resonance Structures 16 2.3 The Two Commandments 17 2.4 Drawing Good Arrows 20 2.5 Formal Charges in Resonance Structures 22 2.6 Drawing Resonance Structures—Step by Step 25 2.7 Drawing Resonance Structures—by Recognizing Patterns 29 2.8 Assessing the Relative Importance of Resonance Structures 36 Chapter 3 Acid–Base Reactions 41 3.1 Factor 1—What Atom is the Charge On? 41 3.2 Factor 2—Resonance 44 3.3 Factor 3—Induction 47 3.4 Factor 4—Orbitals 49 3.5 Ranking the Four Factors 50 3.6 Other Factors 53 3.7 Quantitative Measurement (pKa Values) 54 3.8 Predicting the Position of Equilibrium 54 3.9 Showing a Mechanism 55 Chapter 4 Geometry 57 4.1 Orbitals and Hybridization States 57 4.2 Geometry 60 4.3 Lone Pairs 62 Chapter 5 Nomenclature 64 5.1 Functional Group 65 5.2 Unsaturation 66 5.3 Naming the Parent Chain 67 5.4 Naming Substituents 70 5.5 Stereoisomerism 72 5.6 Numbering 74 5.7 Common Names 78 5.8 Going from a Name to a Structure 79 Chapter 6 Conformations 80 6.1 How to Draw a Newman Projection 80 6.2 Ranking the Stability of Newman Projections 84 6.3 Drawing Chair Conformations 86 6.4 Placing Groups on the Chair 90 6.5 Ring Flipping 93 6.6 Comparing the Stability of Chairs 99 6.7 Don’t Be Confused by the Nomenclature 102 Chapter 7 Configurations 103 7.1 Locating Chiral Centers 103 7.2 Determining the Configuration of a Chiral Center 106 7.3 Nomenclature 113 7.4 Drawing Enantiomers 116 7.5 Diastereomers 120 7.6 Meso Compounds 121 7.7 Drawing Fischer Projections 123 7.8 Optical Activity 127 Chapter 8 Mechanisms 129 8.1 Introduction to Mechanisms 129 8.2 Nucleophiles and Electrophiles 129 8.3 Basicity vs. Nucleophilicity 131 8.4 Arrow-Pushing Patterns for Ionic Mechanisms 133 8.5 Carbocation Rearrangements 138 8.6 Information Contained in a Mechanism 142 Chapter 9 Substitution Reactions 145 9.1 The Mechanisms 145 9.2 Factor 1—The Electrophile (Substrate) 147 9.3 Factor 2—The Nucleophile 149 9.4 Factor 3—The Leaving Group 151 9.5 Factor 4—The Solvent 153 9.6 Using All Four Factors 155 9.7 Substitution Reactions Teach Us Some Important Lessons 156 Chapter 10 Elimination Reactions 157 10.1 The E2 Mechanism 157 10.2 The Regiochemical Outcome of an E2 Reaction 158 10.3 The Stereochemical Outcome of an E2 Reaction 159 10.4 The E1 Mechanism 162 10.5 The Regiochemical Outcome of an E1 Reaction 163 10.6 The Stereochemical Outcome of an E1 Reaction 164 10.7 Substitution vs. Elimination 164 10.8 Determining the Function of the Reagent 165 10.9 Identifying the Mechanism(s) 167 10.10 Predicting the Products 169 Chapter 11 Addition Reactions 172 11.1 Terminology Describing Regiochemistry 172 11.2 Terminology Describing Stereochemistry 174 11.3 Adding H and H 180 11.4 Adding H and X, Markovnikov 183 11.5 Adding H and Br, Anti-Markovnikov 188 11.6 Adding H and OH, Markovnikov 192 11.7 Adding H and OH, Anti-Markovnikov 194 11.8 Synthesis Techniques 198 11.9 Adding Br and Br; Adding Br and OH 204 11.10 Adding OH and OH, Anti 209 11.11 Adding OH and OH, syn 211 11.12 Oxidative Cleavage of an Alkene 213 Summary of Reactions 214 Chapter 12 Alkynes 216 12.1 Structure and Properties of Alkynes 216 12.2 Preparation of Alkynes 218 12.3 Alkylation of Terminal Alkynes 219 12.4 Reduction of Alkynes 221 12.5 Hydration of Alkynes 224 12.6 Keto-Enol Tautomerization 227 12.7 Ozonolysis of Alkynes 232 Chapter 13 Alcohols 234 13.1 Naming and Designating Alcohols 234 13.2 Predicting Solubility of Alcohols 235 13.3 Predicting Relative Acidity of Alcohols 237 13.4 Preparing Alcohols: A Review 239 13.5 Preparing Alcohols via Reduction 240 13.6 Preparing Alcohols via Grignard Reactions 246 13.7 Summary of Methods for Preparing Alcohols 249 13.8 Reactions of Alcohols: Substitution and Elimination 250 13.9 Reactions of Alcohols: Oxidation 253 13.10 Converting an Alcohol into an Ether 255 Chapter 14 Ethers and Epoxides 257 14.1 Introduction to Ethers 257 14.2 Preparation of Ethers 259 14.3 Reactions of Ethers 261 14.4 Preparation of Epoxides 262 14.5 Ring-Opening Reactions of Epoxides 264 Chapter 15 Synthesis 270 15.1 One-Step Syntheses 271 15.2 Multistep Syntheses 283 15.3 Retrosynthetic Analysis 284 15.4 Creating Your Own Problems 285 Detailed Solutions 287 Index 381