| |
| |
| Preface to the Student | |
| |
| |
| Preface to the Instructor | |
| |
| |
| |
| The Basics | |
| |
| |
| |
| Structure and Stability of Organic Compounds | |
| |
| |
| |
| Conventions of Drawing Structures; Grossman's Rule | |
| |
| |
| |
| Lewis Structures; Resonance Structures | |
| |
| |
| |
| Molecular Shape; Hybridization | |
| |
| |
| |
| Aromaticity | |
| |
| |
| |
| Bronsted Acidity and Basicity | |
| |
| |
| |
| pK[subscript a] Values | |
| |
| |
| |
| Tautomerism | |
| |
| |
| |
| Kinetics and Thermodynamics | |
| |
| |
| |
| Getting Started in Drawing a Mechanism | |
| |
| |
| |
| Classes of Overall Transformations | |
| |
| |
| |
| Classes of Mechanisms | |
| |
| |
| |
| Polar Mechanisms | |
| |
| |
| |
| Free-Radical Mechanisms | |
| |
| |
| |
| Pericyclic Mechanisms | |
| |
| |
| |
| Transition-Metal-Catalyzed and -Mediated Mechanisms | |
| |
| |
| |
| Summary | |
| |
| |
| Problems | |
| |
| |
| |
| Polar Reactions under Basic Conditions | |
| |
| |
| |
| Substitution and Elimination at C(sp[superscript 3])-X [sigma] Bonds, Part I | |
| |
| |
| |
| Substitution by the S[subscript N]2 Mechanism | |
| |
| |
| |
| [beta]-Elimination by the E2 and Elcb Mechanisms | |
| |
| |
| |
| Predicting Substitution vs. Elimination | |
| |
| |
| |
| Addition of Nucleophiles to Electrophilic [pi] Bonds | |
| |
| |
| |
| Addition to Carbonyl Compounds | |
| |
| |
| |
| Conjugate Addition; The Michael Reaction | |
| |
| |
| |
| Substitution at C(sp[superscript 2])-X [sigma] Bonds | |
| |
| |
| |
| Substitution at Carbonyl C | |
| |
| |
| |
| Substitution at Alkenyl and Aryl C | |
| |
| |
| |
| Metal Insertion; Halogen-Metal Exchange | |
| |
| |
| |
| Substitution and Elimination at C(sp[superscript 3])-X [sigma] Bonds, Part II | |
| |
| |
| |
| Substitution by the S[subscript RN]1 Mechanism | |
| |
| |
| |
| Substitution by the Elimination-Addition Mechanism | |
| |
| |
| |
| Substitution by the One-Electron Transfer Mechanism | |
| |
| |
| |
| Metal Insertion; Halogen-Metal Exchange | |
| |
| |
| |
| [alpha]-Elimination; Generation and Reactions of Carbenes | |
| |
| |
| |
| Base-Promoted Rearrangements | |
| |
| |
| |
| Migration from C to C | |
| |
| |
| |
| Migration from C to O or N | |
| |
| |
| |
| Migration from B to C or O | |
| |
| |
| |
| Two Multistep Reactions | |
| |
| |
| |
| The Swern Oxidation | |
| |
| |
| |
| The Mitsunobu Reaction | |
| |
| |
| |
| Summary | |
| |
| |
| Problems | |
| |
| |
| |
| Polar Reactions Under Acidic Conditions | |
| |
| |
| |
| Carbocations | |
| |
| |
| |
| Carbocation Stability | |
| |
| |
| |
| Carbocation Generation; The Role of Protonation | |
| |
| |
| |
| Typical Reactions of Carbocations; Rearrangements | |
| |
| |
| |
| Substitution and [beta]-Elimination Reactions at C(sp[superscript 3])-X | |
| |
| |
| |
| Substitution by the S[subscript N]1 and S[subscript N]2 Mechanisms | |
| |
| |
| |
| [beta]-Elimination by the E1 Mechanism | |
| |
| |
| |
| Predicting Substitution vs. Elimination | |
| |
| |
| |
| Electrophilic Addition to Nucleophilic C=C [pi] Bonds | |
| |
| |
| |
| Substitution at Nucleophilic C=C [pi] Bonds | |
| |
| |
| |
| Electrophilic Aromatic Substitution | |
| |
| |
| |
| Aromatic Substitution of Anilines via Diazonium Salts | |
| |
| |
| |
| Electrophilic Aliphatic Substitution | |
| |
| |
| |
| Nucleophilic Addition to and Substitution at Electrophilic [pi] Bonds | |
| |
| |
| |
| Heteroatom Nucleophiles | |
| |
| |
| |
| Carbon Nucleophiles | |
| |
| |
| |
| Summary | |
| |
| |
| Problems | |
| |
| |
| |
| Pericyclic Reactions | |
| |
| |
| |
| Introduction | |
| |
| |
| |
| Classes of Pericyclic Reactions | |
| |
| |
| |
| Polyene MOs | |
| |
| |
| |
| Electrocyclic Reactions | |
| |
| |
| |
| Typical Reactions | |
| |
| |
| |
| Stereospecificity | |
| |
| |
| |
| Stereoselectivity | |
| |
| |
| |
| Cycloadditions | |
| |
| |
| |
| Typical Reactions | |
| |
| |
| |
| Regioselectivity | |
| |
| |
| |
| Stereospecificity | |
| |
| |
| |
| Stereoselectivity | |
| |
| |
| |
| Sigmatropic Rearrangements | |
| |
| |
| |
| Typical Reactions | |
| |
| |
| |
| Stereospecificity | |
| |
| |
| |
| Stereoselectivity | |
| |
| |
| |
| Ene Reactions | |
| |
| |
| |
| Summary | |
| |
| |
| Problems | |
| |
| |
| |
| Free-Radical Reactions | |
| |
| |
| |
| Free Radicals | |
| |
| |
| |
| Stability | |
| |
| |
| |
| Generation from Closed-Shell Species | |
| |
| |
| |
| Typical Reactions | |
| |
| |
| |
| Chain vs. Nonchain Mechanisms | |
| |
| |
| |
| Chain Free-Radical Reactions | |
| |
| |
| |
| Substitution Reactions | |
| |
| |
| |
| Addition and Fragmentation Reactions | |
| |
| |
| |
| Nonchain Free-Radical Reactions | |
| |
| |
| |
| Photochemical Reactions | |
| |
| |
| |
| Reductions and Oxidations with Metals | |
| |
| |
| |
| Cycloaromatizations | |
| |
| |
| |
| Miscellaneous Radical Reactions | |
| |
| |
| |
| 1,2-Anionic Rearrangements; Lone-Pair Inversion | |
| |
| |
| |
| Triplet Carbenes and Nitrenes | |
| |
| |
| |
| Summary | |
| |
| |
| Problems | |
| |
| |
| |
| Transition-Metal-Mediated and -Catalyzed Reactions | |
| |
| |
| |
| Introduction to the Chemistry of Transition Metals | |
| |
| |
| |
| Conventions of Drawing Structures | |
| |
| |
| |
| Counting Electrons | |
| |
| |
| |
| Typical Reactions | |
| |
| |
| |
| Stoichiometric vs. Catalytic Mechanisms | |
| |
| |
| |
| Addition Reactions | |
| |
| |
| |
| Late-Metal-Catalyzed Hydrogenation and Hydrometallation (Pd, Pt, Rh) | |
| |
| |
| |
| Hydroformylation (Co, Rh) | |
| |
| |
| |
| Hydrozirconation (Zr) | |
| |
| |
| |
| Alkene Polymerization (Ti, Zr, Sc, and others) | |
| |
| |
| |
| Cyclopropanation, Epoxidation, and Aziridination of Alkenes (Cu, Rh, Mn, Ti) | |
| |
| |
| |
| Dihydroxylation and Aminohydroxylation of Alkenes (Os) | |
| |
| |
| |
| Nucleophilic Addition to Alkenes and Alkynes (Hg, Pd) | |
| |
| |
| |
| Conjugate Addition Reactions (Cu) | |
| |
| |
| |
| Reductive Coupling Reactions (Ti, Zr) | |
| |
| |
| |
| Pauson-Khand Reaction (Co) | |
| |
| |
| |
| Dotz Reaction (Cr) | |
| |
| |
| |
| Metal-Catalyzed Cycloaddition and Cyclotrimerization (Co, Ni, Rh) | |
| |
| |
| |
| Substitution Reactions | |
| |
| |
| |
| Hydrogenolysis (Pd) | |
| |
| |
| |
| Carbonylation of Alkyl Halides (Pd, Rh) | |
| |
| |
| |
| Heck Reaction (Pd) | |
| |
| |
| |
| Coupling Reactions Between Nucleophiles and C(sp[superscript 2])-X: Kumada, Stille, Suzuki, Negishi, Buchwald-Hartwig, Sonogashira, and Ullmann Reactions (Ni, Pd, Cu) | |
| |
| |
| |
| Allylic Substitution (Pd) | |
| |
| |
| |
| Pd-Catalyzed Nucleophilic Substitution of Alkenes; Wacker Oxidation | |
| |
| |
| |
| Tebbe Reaction (Ti) | |
| |
| |
| |
| Propargyl Substitution in Co-Alkyne Complexes | |
| |
| |
| |
| Rearrangement Reactions | |
| |
| |
| |
| Alkene Isomerization (Rh) | |
| |
| |
| |
| Olefin and Alkyne Metathesis (Ru, W, Mo, Ti) | |
| |
| |
| |
| Elimination Reactions | |
| |
| |
| |
| Oxidation of Alcohols (Cr, Ru) | |
| |
| |
| |
| Decarbonylation of Aldehydes (Rh) | |
| |
| |
| |
| Summary | |
| |
| |
| Problems | |
| |
| |
| |
| Mixed-Mechanism Problems | |
| |
| |
| A Final Word | |
| |
| |
| Index | |