A unique and authoritative text on the fundamental principles of organic synthesis

Understanding Organic Synthesis unveils the logic of organic synthesis by identifying and explaining the similarities and analogies between reactions, as well as the underlying principles that determine how and why various types of organic compounds react. It demonstrates that a wide variety of reactions are either variants or specific examples of a small number of fundamental reactions.

After a brief introduction to the physicochemical principles of organic reactions, Understanding Organic Synthesis discusses:

• Classification of organic reactions into four main categories: nucleophilic, electrophilic, radical, and pericyclic reactions
• The impact of molecular structure on reactivity and the influence of external factors such as energy input, solvents, catalysts, and kinetic versus thermodynamic control
• Classification of nucleophilic agents and electron-deficient partners into five types each, creating 25 possible combinations, which are illustrated by key examples
• Classification of electrophilic agents into five and electron-rich partners into four types, creating 20 possible combinations, which are illustrated by key examples
• Ionic and radical reactions, supplemented by a discussion of pericyclic reactions

Understanding Organic Synthesis is an authoritative text for graduate students and organic chemists in academia and industry to deepen their understanding of reaction pathways that can be used to optimize the synthesis of targeted products or the design of new compounds.

Preface xi

1 Introduction 1

Part I Nucleophilic Reactions 9
2 Reactions of Alkylating Compounds (A) with Nucleophilic Agents (1-5) 13
3 Reactions of Electrophilic Compounds Containing a Double Bond Between Atoms of Different Electronegativity (B) with Nucleophilic Agents (1-5) 49
4 Reactions of Electrophilic Alkenes (C) with Nucleophilic Agents (1-5) 83
5 Reactions of Aromatic Compounds (D) with Nucleophilic Agents (1-5) 93
6 Reactions of Compounds with an Electrophilic Center on a Heteroatom (E) with Nucleophilic Agents (1-5) 105

Part II Electrophilic Reactions 111
7 Interactions of Nucleophilic Compounds (A-C) with Inorganic Cations (1) 123
8 Interactions of Nucleophilic Compounds (A-C) with Uncharged Electrophilic Agents (2) 125
9 Reactions of Nucleophilic Compounds (A-C) with Carbocations (3) 127
10 Reactions of Aromatic Compounds (D) with Electrophilic Agents (1-3) 147
11 Reactions of Nucleophilic Compounds (A-D) with Organic Cations with a Charge on a Heteroatom (4) 177
12 Reactions of Nucleophilic Compounds (A-D) with Electrophilic Carbenes (5) 181
13 Rearrangements of Electron-deficient Nitrogen Compounds 191
14 Reactions of Alkenes with Uncharged Electrophilic Agents 193

Part III Reactions Involving Radicals 195
15 Methods of Radicals Generation 199
16 Substitution Reactions 205
17 Radical Addition to Unsaturated Bonds 217

Part IV Pericyclic Reactions 221
18 Diels-Alder Reaction 223
19 1,3-dipolar Cycloaddition Reactions 229
20 [2+2] Cycloaddition Reactions 237
21 Ene Reactions 239
22 Sigmatropic Rearrangements 243

Further Reading 247
Index 249