Dr. David E. Lewis
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
Key
Terms
Additional Problems
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
Key Terms
Additional Problems
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
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
Key Terms
Additional
Problems
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
Key Terms
Additional
Problems
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
Key Terms
Reaction Synopses
Additional Problems
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
Key Terms
Additional Problems
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
Key Terms
Additional Problems
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
Key
Terms
Reaction Synopses
Additional Problems
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
Key Terms
Reaction Synopses
Additional Problems
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
Key Terms
Reaction Synopses
Additional Problems
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
Key Terms
Reaction Synopses
Additional Problems
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
Key Terms
Reaction Synopses
Additional Problems
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
Key Terms
Reaction Synopses
Additional Problems
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 Summary
Key Terms
Reaction Synopses
Additional Problems
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
Key Terms
Reaction Synopses
Additional Problems
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
Key Terms
Reaction Synopses
Additional Problems
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
Key
Terms
Reaction Synopses
Additional Problems
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
Key Terms
Reaction Synopses
Additional
Problems
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
Key Terms
Reaction Synopses
Additional Problems
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
Key Terms
Reaction Synopses
Additional Problems
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
Key Terms
Reaction Synopses
Additional Problems
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
Key Terms
Additional Problems
E-Book ISBN 9780190609481
David E. Lewis is Professor of Chemistry at the University of Wisconsin-Eau Claire.
Organic Chemistry - Jonathan Clayden, Nick Greeves and Stuart Warren
Scientific Writing and Communication - Angelika Hofmann
