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<p>PREFACE xi</p> <p>ACKNOWLEDGEMENTS xiii</p> <p>ABOUT THE AUTHOR xv</p> <p><b>1. Introduction 1</b></p> <p>1.1 Definition of Arrow-Pushing 1</p> <p>1.2 Functional Groups 5</p> <p>1.3 Nucleophiles and Leaving Groups 7</p> <p>1.4 Summary 8</p> <p>Problems 9</p> <p><b>2. Free Radicals 19</b></p> <p>2.1 What Are Free Radicals? 19</p> <p>2.2 How Are Free Radicals Formed? 21</p> <p>2.2.1 Free Radical Initiators 22</p> <p>2.2.2 Electron Transfer 23</p> <p>2.3 Free Radical Stability 23</p> <p>2.4 What Types of Reactions Involve Free Radicals? 25</p> <p>2.4.1 Halogenation Reactions 26</p> <p>2.4.2 Polymerization Reactions 28</p> <p>2.4.3 Oxidation Reactions 30</p> <p>2.5 Summary 31</p> <p>Problems 32</p> <p><b>3. Acids 37</b></p> <p>3.1 What Are Acids? 37</p> <p>3.2 What Is Resonance? 38</p> <p>3.3 How Is Acidity Measured? 41</p> <p>3.4 Relative Acidities 42</p> <p>3.5 Inductive Effects 47</p> <p>3.6 Inductive Effects and Relative Acidities 49</p> <p>3.7 Relative Acidities of Hydrocarbons 50</p> <p>3.8 Summary 51</p> <p>Problems 52</p> <p><b>4. Bases and Nucleophiles 61</b></p> <p>4.1 What Are Bases? 61</p> <p>4.2 What Are Nucleophiles? 66</p> <p>4.3 Leaving Groups 70</p> <p>4.4 Summary 70</p> <p>Problems 71</p> <p><b>5. SN2 Substitution Reactions 81</b></p> <p>5.1 What Is An SN2 Reaction? 81</p> <p>5.2 What Are Leaving Groups? 83</p> <p>5.3 Where Can SN2 Reactions Occur? 84</p> <p>5.4 SN2′ Reactions 85</p> <p>5.5 Summary 88</p> <p>Problems 89</p> <p><b>6. SN1 Substitution Reactions 97</b></p> <p>6.1 What Is An SN1 Reaction? 97</p> <p>6.2 How Are SN1 Reactions Initiated? 98</p> <p>6.3 The Carbocation 99</p> <p>6.3.1 Molecular Structure and Orbitals 100</p> <p>6.3.2 Stability of Carbocations 103</p> <p>6.4 Carbocation Rearrangements 105</p> <p>6.4.1 1,2-Hydride Shifts 105</p> <p>6.4.2 1,2-Alkyl Shifts 106</p> <p>6.4.3 Preventing Side Reactions 109</p> <p>6.5 Summary 109</p> <p>Problems 110</p> <p><b>7. Elimination Reactions 115</b></p> <p>7.1 E1 Eliminations 115</p> <p>7.2 E1cB Eliminations 118</p> <p>7.3 E2 Eliminations 120</p> <p>7.4 How Do Elimination Reactions Work? 121</p> <p>7.5 E1cB Eliminations Versus E2 Eliminations 124</p> <p>7.6 Summary 124</p> <p>Problems 126</p> <p><b>8. Addition Reactions 133</b></p> <p>8.1 Addition of Halogens to Double Bonds 133</p> <p>8.2 Markovnikov’s Rule 135</p> <p>8.3 Additions to Carbonyls 137</p> <p>8.3.1 1,2-Additions 137</p> <p>8.3.2 1,4-Additions 138</p> <p>8.3.3 Addition–Elimination Reactions 141</p> <p>8.4 Summary 143</p> <p>Problems 144</p> <p><b>9. Carbenes 153</b></p> <p>9.1 What Are Carbenes? 153</p> <p>9.2 How Are Carbenes Formed? 154</p> <p>9.3 Reactions with Carbenes 156</p> <p>9.3.1 Carbene Dimerization 156</p> <p>9.3.2 Cyclopropanation Reactions 157</p> <p>9.3.3 O-H Insertion Reactions 161</p> <p>9.4 Carbenes Versus Carbenoids 162</p> <p>9.5 Summary 163</p> <p>Problems 164</p> <p><b>10. Pericyclic Reactions 171</b></p> <p>10.1 What Are Pericyclic Reactions? 171</p> <p>10.2 Electrocyclic Reactions 172</p> <p>10.3 Cycloaddition Reactions 175</p> <p>10.3.1 The Diels–Alder Reaction 175</p> <p>10.3.2 The Ene Reaction 178</p> <p>10.3.3 Dipolar Cycloaddition Reactions 180</p> <p>10.4 Sigmatropic Reactions 182</p> <p>10.4.1 The Cope Rearrangement 183</p> <p>10.4.2 The Claisen Rearrangement 184</p> <p>10.5 Summary 187</p> <p>Problems 189</p> <p><b>11. Moving Forward 195</b></p> <p>11.1 Functional Group Manipulations 195</p> <p>11.2 Name Reactions 196</p> <p>11.3 Reagents 208</p> <p>11.4 Final Comments 208</p> <p>Problems 209</p> <p>Appendix 1. pKa Values of Protons Associated with Common Functional Groups 219</p> <p>Appendix 2. Answers and Explanations to Problems 223</p> <p>Chapter 1 Solutions 224</p> <p>Chapter 2 Solutions 234</p> <p>Chapter 3 Solutions 241</p> <p>Chapter 4 Solutions 258</p> <p>Chapter 5 Solutions 270</p> <p>Chapter 6 Solutions 285</p> <p>Chapter 7 Solutions 293</p> <p>Chapter 8 Solutions 303</p> <p>Chapter 9 Solutions 318</p> <p>Chapter 10 Solutions 334</p> <p>Chapter 11 Solutions 347</p> <p>Appendix 3. Student Reaction Glossary 369</p> <p>Index 373</p> <p>Periodic Table of Elements 401</p>

<p><b>DANIEL E. LEVY, PhD</b>, is the owner of DEL BioPharma LLC, USA. He previously worked at Glycomed, COR Therapeutics, Scios, and Intradigm. Dr. Levy developed, with Dr. Péter Fügedi, short courses entitled "Modern Synthetic Carbohydrate Chemistry" and "The Organic Chemistry of Sugars." He has three books to his credit, including the rst edition of <i>Arrow-Pushing in Organic Chemistry</i> (Wiley, 2008). He received his bachelors in chemistry from the University of California– Berkeley and his doctorate in organic chemistry from the Massachusetts Institute of Technology.</p>

<p><b>Reviews of the First Edition:</b></p> <p>"... fills an important gap in undergraduate education, and I would encourage every instructor of organic chemistry to seriously evaluate this text as a substantive aid. This book is definitely well worth its price!"<BR><b><i>Angewandte Chemie International Edition</i></b> <p>"... serves as a valuable workbook to counteract student memorization and compartmentalization of organic chemistry material. ... a great supplemental resource to guide the novice organic chemistry student down the path to a true understanding of the subject."<BR><b><i>Chemical Education Today</i></b> <p>"The high point of the book is the provision of a large number of carefully targeted problems at the end of each chapter, complete with well-explained worked answers. I am sure that these will be highly useful to students...."<BR><b><i>Physical Sciences Centre Reviews</i></b> <p>Most organic chemistry texts intimidate through sheer size, encyclopedic presentation of reactions, and a huge amount of material to memorize. Building on the legacy of a highly successful first edition, this book teaches a better and easier way to approach the subject—the arrow-pushing strategy that reduces organic chemistry to the study of interactions between organic acids and bases and builds from there. To help the students discouraged by the belief that this topic cannot be mastered without signi cant memorization, the 2nd edition of <i>Arrow-Pushing in Organic Chemistry</i> serves as a handy supplement for understanding the subject. New and updated chapters cover free radicals, carbenes, and pericyclic reaction mechanisms. Additionally, problem sets for each chapter emphasize the important concepts, reinforce the reader's knowledge of chemistry, and introduce other aspects of organic chemistry discussed in latter chapters or in a student's class. <p>Key benefits and features of the 2nd edition include: <ul><li>New chapters, an expanded index, and additional problem sets complete with detailed solutions</li> <li>Introduction of ionic and nonionic reactive species and reaction mechanisms</li> <li>Strategies to predict reactive species, sites of reactions, and reaction products</li> <li>A solid foundation upon which organic chemistry students can advance with con dence</li></ul>

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