Advanced Organic Chemistry

by Lewis, David E.

• ISBN13: 9780199758975
• ISBN10: 0199758972
• Format: Paperback
• Copyright: 2015-09-15
• Publisher: Oxford University Press

Summary

Written by a master teacher, Advanced Organic Chemistry presents a clear, concise, and complete overview of the subject that is ideal for both advanced undergraduate and graduate courses. In contrast with many other books, this volume is a true textbook, not a reference book.

FEATURES

* Uses a unique method of categorizing organic reactions that is based on reactivity principles rather than mechanism or functional group, enabling students to see reactivity patterns in superficially widely disparate systems

* Emphasizes fundamental physical organic concepts that reinforce themes, giving students the foundation to understand both mechanisms and synthesis

* Covers asymmetric methodologies, a topic that is now ubiquitous in the current literature

* Numerous in-chapter worked problems and end-of-chapter additional exercises allow students to apply concepts as they learn them

* More than 2500 references to the primary literature in the body of the book(along with another 750 references in the problems) encourage students to become familiar with real scholarship as they master the concepts

* Brief historical vignettes about relevant chemists reinforce a historical and humanizing approach to learning science

Author Biography

David E. Lewis is Professor of Chemistry at the University of Wisconsin-Eau Claire.

Table of Contents

Chapter 1. The Fundamentals Revisited: Structure, Bonding, and Reactivity
1.1 Organic Structure: A Brief History
1.2 Proton Transfers Revisited: Acids and Bases
1.3 Reactions and Reaction Mechanisms: "Electron Pushing"
1.4 Resonance
1.5 Spectroscopy and Chromatography
Chapter Summary and Glossary of Terms
Additional Problems
Chapter 2. Stereochemistry
2.1 Stereoisomers and Chirality
2.2 Absolute Configuration
2.3 Optical Purity and Configuration
2.4 Conformation
2.5 An Introduction to Asymmetric Synthesis: Asymmetric Induction
2.6 How Well Did It Go? Measuring Enantiomer Ratios
2.7 Chirality at Atoms Other Than Carbon: Inversion of Pyramidal Centers
Chapter Summary and Glossary of Terms
Additional Problems
Chapter 3. Organic Short-hand: Acronyms and Name Reactions
3.1 Organic Synthesis: A Brief Introduction
3.2 Name Reactions: A Historical Overview
3.3 Acronyms and Abbreviations
Chapter 4. Orbitals and Reactivity
4.1 Introduction
4.2 Atomic Orbitals: The History of the Modern Atomic Model
4.3 Covalent Bonding and Molecular Orbitals
4.4 Chemical Reactions: Frontier Orbitals
Chapter Summary and Glossary of Terms
Additional Problems
Chapter 5. Frontier Orbitals and Chemical Reactions
5.1 Using Frontier Orbitals (FMOs) to Categorize Reactions and Reagents
5.2 Categorizing Reactions Using FMP Pairings
5.3 Stereoelectronic Effects
5.4 Radical Reactions
Chapter Summary and Glossary of Terms
Additional Problems
Chapter 6. Synthetic Reactions I: Pericyclic Reactions and Conservation of Orbital Symmetry
6.1 Introduction
6.2 Molecular Orbitals of Conjugated Systems; Orbital Symmetry
6.3 Qualitative Perturbation Theory: Approximating Frontier Orbitals of Substituted Alkenes and Dienes
6.4 Sigmatropic Rearrangements
6.5 Cycloaddition Reactions
6.6 Ene, Retro-ene and Similar Reactions
6.7 Combining Pericyclic Reactions in Sequence
Chapter Summary and Glossary of Terms
Reaction Synopses
Additional Problems
Chapter 7. Aromaticity
7.1 Benzene: The Beginning
7.2 Aromaticity and Antiaromaticity: The H:uckel Molecular Orbital Model of Cyclic Polyenes
7.3 How Does One Measure Aromaticity? Criteria for Aromaticity and its Quantification
7.4 M:obius Aromaticity
7.5 Homoaromaticity
7.6 The Rest of the Story . . . The History and Mythology of Benzene
Chapter Summary and Glossary of Terms
Additional Problems
Chapter 8. Physical Organic Chemistry and Reaction Mechanisms
8.1 Introduction
8.2 Solvents and Solubility
8.3 Reaction Kinetics
8.4 Activation Parameters from Kinetic Studies
8.5 Correlating Similar Reactions: Linear Free Energy Relationships
8.6 Isotope and Element Effects
8.7 Trapping and Crossover Experiments
8.8 The Variable Transition State and the Concept of the Mechanistic Spectrum
8.9 Using Regiochemistry and Stereochemistry
8.10 The Reactivity-Selectivity Principle
Chapter Summary and Glossary of Terms
Additional Problems
Chapter 9. Reactive Intermediates I: Carbocations
9.1 Carbocations
9.2 Rearrangements
9.3 Neighboring Group Participation
9.4 Non-classical Carbocations
9.5 Methods for Generating Carbocations
Chapter Summary and Glossary of Terms
Reaction Synopses
Additional Problems
Chapter 10. Synthetic Reactions II: Using Carbocations for C--C Bond Formation in Synthesis
10.1 Introduction
10.2 The Friedel-Crafts Reaction
10.3 Formylation
10.4 Addition of Stabilized Cations to Alkenes: The Prins, Mannich, and Mukaiyama Reactions
Chapter Summary and Glossary of Terms
Reaction Synopses
Additional Problems
Chapter 11. Reactive Intermediates II: Carbanions and Their Reactivity
11.1 Carbanions: Introduction and Overview
11.2 Simple Organometallic Nucleophiles: Metal Alkyls
11.3 Carbanions Stabilized by Heteroatoms
11.4 Formation of Enolate Anions
11.5 Rearrangements of Carbanions
Chapter Summary and Glossary of Terms
Reaction Synopses
Additional Problems
Chapter 12. Synthetic Reactions III: Synthetic Reactions of Carbon Nucleophiles, Part 1
12.1 Carbon-Carbon Bond Formation: Carbon Nucleophiles and Electrophiles
12.2 Substitution and Addition With Metal Alkyl Reagents Having C-M ? Bonds
12.3 Metal Enolates: Versatile Carbon Nucleophiles
12.4 The Aldol Addition Reaction
12.5 Conjugate Addition of Enolates and Similar Compounds
12.6 Azaenol Derivatives: Imines, Hydrazones and Enamines
Chapter Summary and Glossary of Terms
Reaction Synopses
Additional Problems
Chapter 13. Reactive Intermediates III: Free Radicals, Carbenes, Arynes and Nitrenes
13.1 Free Radicals
13.2 Carbenes
13.3 Nitrenes
13.4 Arynes
Chapter Summary and Glossary of Terms
Reaction Synopses
Additional Problems
Chapter 14. Synthetic Reactions IV: Applications of Free Radical Chemistry in Synthesis
14.1 Methods for Site-Specific Generation of Free Radicals
14.2 Reactions of Free Radicals
14.3 Reactions of Free Radicals Useful for Synthesis
14.4 Additions and Cyclizations of Free Radicals
14.5 Diradicals: Formation and Uses in Synthesis
Chapter Summary and Glossary of Terms
Reaction Synopses
Additional Problems
Chapter 15. Organic Synthesis I: Retrosynthetic Analysis, Protecting Groups, and the Strategy of Organic Synthesis
15.1 What is Organic Synthesis?
15.2 Organic Reactions: Tools of the Organic Chemist
15.3 Retrosynthetic Analysis: An Introduction to the Vocabulary and Strategy of Organic Synthesis
15.4 Applying RetrosyntheticAnalysis to a Real Example
15.5 Selectivity Revisited
15.6 Protection of Alcohols
15.7 Protection of Aldehydes, Ketones, and Carboxylic Acids
15.8 Protection of Amines
15.9 Protecting Groups for Hydrocarbons
Chapter Review and Glossary of Terms
Reaction Synopses
Additional Problems
Chapter 16. Synthetic Reactions V: Condensations and Cascade Reactions of Carbon Nucleophiles
16.1 Addition, Condensation, Cascade Reactions: Definitions
16.2 The Aldol Condensation and Related Reactions
16.3 Condensations Where the Initial Adduct is Intercepted
16.4 The Claisen Condensation and Related Reactions
16.5 The Wittig, Horner-Wadsworth-Emmons, and Related Reactions
16.6 Cascade Reactions Initiated by Carbon Nucleophiles
Chapter Summary and Glossary of Terms
Reaction Synopses
Additional Problems
Chapter 17. Synthetic Reactions VI: Catalytic Reactions for C-C Bond Formation
17.1 Catalysis and Green Chemistry
17.2 Bonding in Organometallic Complexes
17.3 Basic Organometallic Reactions: Reactions at the Metal
17.4 Basic Organometallic Reactions: Reactions at the Ligand
17.5 Hydrometalation: Making the Organometallic Reagents by Addition
17.6 Palladium-Catalyzed Substitution: The Tsuji-Trost and Buchwald-Hartwig Reactions
17.7 Cross-Coupling Reactions to Form C--C Bonds
Chapter Summary and Glossary of Terms
Reaction Synopses
Additional Problems
Chapter 18. Redox Reactions I: Oxidation
18.1 Introduction
18.2 Overview of Oxidation
18.3 Oxidation of Alcohols to Aldehydes and Ketones with Stoichiometric Metal-Based Reagents
18.4 Oxidation of Alcohols Using Non-Metal-Based Reagents
18.5 Oxidations to Carboxylic Acids
18.6 Oxidation of Ethers and Amines
18.7 Oxidative Rearrangements
18.8 Oxidation of Unsaturated Hydrocarbons
18.9 Oxidative Cleavage of Carbon-Carbon Bonds
18.10 Oxidative Substitution of Carbon-Hydrogen ? Bonds
18.11 Oxidation of Alkanes
18.12 A Catalogue of Oxidation Reactions: Oxidation at a Glance
Chapter Summary and Glossary of Terms
Reaction Synopses
Additional Problems
Chatper 19. Redox Reactions II: Reduction with Molecular Hydrogen or its Equivalent
19.1 Overview of Reduction
19.2 Catalytic Hydrogenation
19.3 Hydrogenlysis
Chapter Summary and Glossary of Terms
Reaction Synopses
Additional Problems
Chapter 20. Redox III: Reduction with Complex Metal Hydrides and Active Metals
20.1 Reductions with Metal Hydrides
20.2 Reduction by Hydrogen Transfer from Carbon
20.3 Stereochemistry and Stereoselectivity in Hydride Reduction
20.4 Reduction Using Metals
20.5 Reduction of Carbonyl Compounds to Hydrocarbons
20.6 A Catalogue of Reduction Reactions: Reduction at a Glance
Chapter Summary and Glossary of Terms
Reaction Synopses
Additional Problems
Chapter 21. Aymmetric Oxidation and Reduction
21.1 Asymmetric Redox Reactions: An Overview
21.2 Sharpless Asymmetric Epoxidation of Allylic Alcohols
21.3 Asymmetric Epoxidation of Unfunctionalized Alkenes
21.4 Oxidation With Chiral Three-membered Heterocycles
21.5 Asymmetric Dihydroxylation
21.6 Kinetic Resolution of Alcohols
21.7 Enantioselective Insertion into C--C and C--H Bonds
21.8 Asymmetric Hydrogenation
21.9 Asymmetric Reductions with Metal Hydrides and Metal Alkyls
21.10 Enzymes: Biocatalysis of Redox Reactions
Chapter Summary and Glossary of Terms
Reaction Synopses
Additional Problems
Chapter 22. Main-Group Organic Chemistry: Silicon, Phosphorus, Sulfur, Selenium and Tin
22.1 Introduction
22.2 Silanes and Stannanes as Directing Groups: Carbocation Chemistry
22.3 Heteroatom-Centered Nucleophiles: Silyllithiums, Stannyllithiums , Sulfides and Selenides
22.4 Reactions of Organophosphorus, Organosulfur and Organoselenium Compounds
Chapter Summary and Glossary of Terms
Reaction Synopses
Additional Problems
Chapter 23. Modern Asymmetric Synthesis
23.1 Controlling Absolute Stereochemistry
23.2 Asymmetric Synthesis with Chiral Auxiliaries: Additions
23.3 Asymmetric Substitution at Carbon: Alkylation of Enolates and Related Nucleophiles
23.4 Catalytic Asymmetric Synthesis
23.5 Representative Asymmetric Syntheses
Chapter Summary and Glossary of Terms
Additional Problems