Arrow-Pushing in Organic Chemistry: An Easy Approach to Understanding Reaction Mechanisms / Edition 2

by Daniel E. Levy

Overview

Organic chemistry is required coursework for degrees in life, food, and medical sciences.  To help the students discouraged by the belief that this topic cannot be mastered without significant memorization, Arrow Pushing in Organic Chemistry serves as a handy supplement for understanding the subject.

•    Includes new chapters, an expanded index, and additional problem sets complete with detailed solutions
•    Focuses on understanding the mechanics and logic of organic reaction mechanisms
•    Introduces ionic and non-ionic reactive species and reaction mechanisms
•    Teaches strategies to predict reactive species, sites of reactions, and reaction products
•    Provides a solid foundation upon which organic chemistry students can advance with confidence

Product Details

ISBN-13:	9781118991329
Publisher:	Wiley
Publication date:	03/06/2017
Edition description:	2nd ed.
Pages:	424
Product dimensions:	7.00(w) x 9.90(h) x 0.80(d)

About the Author

DANIEL E. LEVY, PhD, 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 Arrow-Pushing in Organic Chemistry (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.

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Table of Contents

PREFACE xi

ACKNOWLEDGEMENTS xiii

ABOUT THE AUTHOR xv

1. Introduction 1

1.1 Definition of Arrow-Pushing 1

1.2 Functional Groups 5

1.3 Nucleophiles and Leaving Groups 7

1.4 Summary 8

Problems 9

2. Free Radicals 19

2.1 What Are Free Radicals? 19

2.2 How Are Free Radicals Formed? 21

2.2.1 Free Radical Initiators 22

2.2.2 Electron Transfer 23

2.3 Free Radical Stability 23

2.4 What Types of Reactions Involve Free Radicals? 25

2.4.1 Halogenation Reactions 26

2.4.2 Polymerization Reactions 28

2.4.3 Oxidation Reactions 30

2.5 Summary 31

Problems 32

3. Acids 37

3.1 What Are Acids? 37

3.2 What Is Resonance? 38

3.3 How Is Acidity Measured? 41

3.4 Relative Acidities 42

3.5 Inductive Effects 47

3.6 Inductive Effects and Relative Acidities 49

3.7 Relative Acidities of Hydrocarbons 50

3.8 Summary 51

Problems 52

4. Bases and Nucleophiles 61

4.1 What Are Bases? 61

4.2 What Are Nucleophiles? 66

4.3 Leaving Groups 70

4.4 Summary 70

Problems 71

5. SN2 Substitution Reactions 81

5.1 What Is An SN2 Reaction? 81

5.2 What Are Leaving Groups? 83

5.3 Where Can SN2 Reactions Occur? 84

5.4 SN2′ Reactions 85

5.5 Summary 88

Problems 89

6. SN1 Substitution Reactions 97

6.1 What Is An SN1 Reaction? 97

6.2 How Are SN1 Reactions Initiated? 98

6.3 The Carbocation 99

6.3.1 Molecular Structure and Orbitals 100

6.3.2 Stability of Carbocations 103

6.4 Carbocation Rearrangements 105

6.4.1 1,2-Hydride Shifts 105

6.4.2 1,2-Alkyl Shifts 106

6.4.3 Preventing Side Reactions 109

6.5 Summary 109

Problems 110

7. Elimination Reactions 115

7.1 E1 Eliminations 115

7.2 E1cB Eliminations 118

7.3 E2 Eliminations 120

7.4 How Do Elimination Reactions Work? 121

7.5 E1cB Eliminations Versus E2 Eliminations 124

7.6 Summary 124

Problems 126

8. Addition Reactions 133

8.1 Addition of Halogens to Double Bonds 133

8.2 Markovnikov’s Rule 135

8.3 Additions to Carbonyls 137

8.3.1 1,2-Additions 137

8.3.2 1,4-Additions 138

8.3.3 Addition–Elimination Reactions 141

8.4 Summary 143

Problems 144

9. Carbenes 153

9.1 What Are Carbenes? 153

9.2 How Are Carbenes Formed? 154

9.3 Reactions with Carbenes 156

9.3.1 Carbene Dimerization 156

9.3.2 Cyclopropanation Reactions 157

9.3.3 O-H Insertion Reactions 161

9.4 Carbenes Versus Carbenoids 162

9.5 Summary 163

Problems 164

10. Pericyclic Reactions 171

10.1 What Are Pericyclic Reactions? 171

10.2 Electrocyclic Reactions 172

10.3 Cycloaddition Reactions 175

10.3.1 The Diels–Alder Reaction 175

10.3.2 The Ene Reaction 178

10.3.3 Dipolar Cycloaddition Reactions 180

10.4 Sigmatropic Reactions 182

10.4.1 The Cope Rearrangement 183

10.4.2 The Claisen Rearrangement 184

10.5 Summary 187

Problems 189

11. Moving Forward 195

11.1 Functional Group Manipulations 195

11.2 Name Reactions 196

11.3 Reagents 208

11.4 Final Comments 208

Problems 209

Appendix 1. pKa Values of Protons Associated with Common Functional Groups 219

Appendix 2. Answers and Explanations to Problems 223

Chapter 1 Solutions 224

Chapter 2 Solutions 234

Chapter 3 Solutions 241

Chapter 4 Solutions 258

Chapter 5 Solutions 270

Chapter 6 Solutions 285

Chapter 7 Solutions 293

Chapter 8 Solutions 303

Chapter 9 Solutions 318

Chapter 10 Solutions 334

Chapter 11 Solutions 347

Appendix 3. Student Reaction Glossary 369

Index 373

Periodic Table of Elements 401

What People are Saying About This

From the Publisher

"Arrow Pushing in Organic Chemistry is not meant to replace a traditional textbook, a point that Levy makes clear in the preface. Rather, the text serves as a valuable workbook to counteract student memorization and compartmentalization of organic chemistry material. Review topics are presented in the context of new information, and major concepts are constantly reiterated and highlighted. Levy's book is a great supplemental resource to guide the novice organic chemistry student down the path to a true understanding of the subject." (Chemical Education Today, June 2010)

"The discussion of each class or reaction is both readable and informative and normally includes comparison of relative rates of similar reactions to demonstrate concepts such as nucleophilicity or steric hindrance. The major strength of the book involved the inclusion of problems at the end of each chapter. These are coupled with a set of very well discussed answers provided in the appendix. The problems fit well with the topic under discussion at each stage and the mechanistic answers and associated explanations are of a high quality. . . this text will make a useful addition to a university library or the supplementary reading list of a first year organic chemistry course." (Reviews, 1 December 2009)

"Does serve as a good support text for a more comprehensive organic text book. 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 who wish to practice the use of the ‘curry arrow." (Physical Sciences Centre Reviews, 1 December 2009)

"The most valuable materials in the book are the many solved problems." (Journal of Medicinal Chemistry, January 22, 2009)

"Arrow Pushing in Organic Chemistry 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!" (Angewandte Chemie International Edition, January 12, 2009)

The first two semesters of organic chemistry are almost universally daunting to the student. The use of organic reaction mechanisms has greatly reduced the memorization, but most organic books skimp a bit on explaining how to write a clear reaction mechanism in order to limit their already gargantuan size (and cost). Along comes Arrow Pushing in Organic Chemistry by Levy (director of synthetic chemistry, Intradigm Corp.), a book that tries to clearly and succinctly explain writing organic mechanisms to these students. It does an excellent job in this. The work includes a large number of challenging end-of-chapter problems, with complete answers in the appendix (this appendix accounts for nearly half of the book). These problems may be too challenging for the typical sophomore organic student who may rely too much on the complete answers. This monograph is an excellent supplement but not a replacement for sophomore-level organic chemistry course resources. Most other monographs on organic reaction mechanisms are geared for the advanced undergraduate or graduate student. Summing Up: Recommended. Lower-division undergraduate organic chemistry students. (J.H. Glans, Sacred Heart University, Choice, February 2009)

Editorial Reviews

"Arrow Pushing in Organic Chemistry is not meant to replace a traditional textbook, a point that Levy makes clear in the preface. Rather, the text serves as a valuable workbook to counteract student memorization and compartmentalization of organic chemistry material. Review topics are presented in the context of new information, and major concepts are constantly reiterated and highlighted. Levy's book is a great supplemental resource to guide the novice organic chemistry student down the path to a true understanding of the subject." (Chemical Education Today, June 2010)

"The discussion of each class or reaction is both readable and informative and normally includes comparison of relative rates of similar reactions to demonstrate concepts such as nucleophilicity or steric hindrance. The major strength of the book involved the inclusion of problems at the end of each chapter. These are coupled with a set of very well discussed answers provided in the appendix. The problems fit well with the topic under discussion at each stage and the mechanistic answers and associated explanations are of a high quality. . . this text will make a useful addition to a university library or the supplementary reading list of a first year organic chemistry course." (Reviews, 1 December 2009)

"Does serve as a good support text for a more comprehensive organic text book. 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 who wish to practice the use of the ‘curry arrow." (Physical Sciences Centre Reviews, 1 December 2009)

"The most valuable materials in the book are the many solved problems." (Journal of Medicinal Chemistry, January 22, 2009)

"Arrow Pushing in Organic Chemistry 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!" (Angewandte Chemie International Edition, January 12, 2009)

The first two semesters of organic chemistry are almost universally daunting to the student. The use of organic reaction mechanisms has greatly reduced the memorization, but most organic books skimp a bit on explaining how to write a clear reaction mechanism in order to limit their already gargantuan size (and cost). Along comes Arrow Pushing in Organic Chemistry by Levy (director of synthetic chemistry, Intradigm Corp.), a book that tries to clearly and succinctly explain writing organic mechanisms to these students. It does an excellent job in this. The work includes a large number of challenging end-of-chapter problems, with complete answers in the appendix (this appendix accounts for nearly half of the book). These problems may be too challenging for the typical sophomore organic student who may rely too much on the complete answers. This monograph is an excellent supplement but not a replacement for sophomore-level organic chemistry course resources. Most other monographs on organic reaction mechanisms are geared for the advanced undergraduate or graduate student. Summing Up: Recommended. Lower-division undergraduate organic chemistry students. (J.H. Glans, Sacred Heart University, Choice, February 2009)

From the Publisher