Short description:

Organic chemistry is the science of carbon-containing compounds. There are four major types of reactive intermediates in organic chemistry: carbocations, carboanions, radicals and carbenes. Therefore, carbocation chemistry is not only fundamental to the advancement of organic chemistry, it also has found widespread applications in organic synthesis. It is not an exaggeration to say that carbocation chemistry is part of the foundation of organic chemistry. This book provides a panoramic view of carbocation chemistry with an emphasis on synthetic applications.

Long description:

Carbocation chemistry is not only fundamental to the advancement of organic chemistry, it also has found widespread applications in organic synthesis. It is not an exaggeration to say that carbocation chemistry is part of the foundation of organic chemistry. Carbocation Chemistry: Applications in Organic Synthesis provides a panoramic view of carbocation chemistry with an emphasis on synthetic applications.

This book is an invaluable tool for organic, medicinal and analytical chemists, including those working in biochemistry as well as the petroleum, plastics and pharmaceutical industries. It is also suitable for upper level undergraduates and graduates in organic chemistry, biochemistry and medicinal chemistry.

Table of Contents:

Chapter 1. Introduction

1. Nomenclature, Structure, and Stability


2. Generation of Carbocations


3. The Non-Classical Ion Controversy


4. Electrophilic Addition to Alkenes


5. Electrophilic Aromatic Substitution


6. Elimination reactions


7. Rearrangement Reactions of Carbocations


8. References

Chapter 2. Nucleophilic Aliphatic Substitution ? S_N1

1. Introduction


2. -Activated Alcohols?Br?nsted Acids


3. -Activated Alcohols?Lewis Acids


4. Alkylation of Aldehydes and Ketones


5. Glycosylation


6. Friedel?Crafts Alkylation and Acylation


7. Electrophilic Fluorination Using Fluoronium Ion


8. Miscellaneous S_N1-related Reactions


9. References

Chapter 3. Nucleophilic Aliphatic Substitution ? S_N2

1. Construction of Quaternary Stereogenic Centers


2. Sulfur Chemistry


3. Organometallic Chemistry


4. Macrocyclization


5. Glycosylation


6. Nucleoside Analogues


7. N-Alkylation


8. Cyclotetraphosphazenes


9. Conformationally Locked Tetrahydropyran Ring


10. The Ionic Liquid Effect


11. Silver Chemistry


12. References

Chapter 4. Electrophilic Addition to Alkenes

1. Introduction


2. Cyclopropanation


3. Hydroboration/Oxidation


4. The Pauson?Khand Reaction


5. Prins Reaction


6. Schmidt Reaction


7. Halogenation


8. Oxymercuration/Reduction


9. Epoxidation


10. Gold-Catalyzed Alkyne Hydration


11. Conclusion


12. References

Chapter 5. Electrophilic Aromatic Substitution

1. Introduction


2. Nitration


3. Halogenation


4. Friedel?Crafts Alkylation


5. Friedel?Crafts Acylation


6. Applications of Friedel?Crafts Reaction on Total Synthesis


7. Miscellaneous Electrophilic Aromatic Substitution Reactions


8. References

Chapter 6. Fragmentation and Rearrangement Reactions

1. Claisen Rearrangements


2. Cope Rearrangements


3. Cope Rearrangements


4. Aldehyde (or Ketone) Formation Rearrangements


5. Carboxylic Acid Formation Rearrangements


6. Alcohol Formation Rearrangements


7. Amine Formation Rearrangement


8. Amides


9. Hydrocarbon Rearrangements


10. Oxacyclic, Carbocyclic, Oxazoles, Tetrahydrapuran and Tetrahydropuran Formation Rearrangements


11. Rearrangements resulting in less common functional groups


12. Fragmentations


13. References