Preface to the Student
Preface to the Instructor
1 The Basics
1.1 Structure and Stability of Organic Compounds
1.1.1 Conventions of Drawing Structures；Grossman’S Rule
1.1.2 Lewis Structures；Resonance Structures
1.1.3 Molecular Shape；Hybridization
1.1.4 Aromaticity
1.2 BrCnsted Acidity and Basicity
1.2.1 PK Values
1.2.2 Tautomerism
1.3 Kinetics and Thermodynamics
1.4 Getting Started in Drawing a Mechanism
1.5 Classes of Overall Transformations
1.6 Classes of Mechanisms
1.6.1 Polar Mechanisms
1.6.2 Free.Radical Mechanisms
1.6.3 Pericyclic Mechanisms
1.6.4 Transition-Metal-Catalyzed and-Mediated Mechanisms
1.7 Summary
Problems
2 Polar Reactions under Basic Conditions
2.1 Substitution and Elimination at C（sp3）—X Bonds.Part I
2.1.1 Substitution by the SN2 Mechanism
2.1.2 Elimination by the E2 and Elcb Mechanisms
2.1.3 Predicting Substitution VS.Elimination
2.2 Addition of Nucleophiles to Electrophilic仃Bonds
2.2.1 Addition to Carbonyl Compounds
2.2.2 Conjugate Addition；The Michael Reaction
2.3 Substitution at C（sp2）一X Bouds
2.3.1 Substitution at Carbonyl C
2.3.2 Substitution at Alkenyl and Aryl C
2.3.3 Metal Insertion；Halogen-Metal Exchange
2.4 Substitution and Elimination at C（sp3）-X Bonds，Part II
2.4.1 Substitution by the SRNl Mechanism
2.4.2 Substitution by the Elimination-Addition Mechanism
2.4.3 Substitution by the One-Electron Transfer Mechanism
2.4.4 Metal Insertion；Halogen一Metal Exchange
2.4.5 Ol-Elimination；Generation and Reactions of Carbenes
2.5 Base-Promoted Rearrangements
2.5.1 Migration from C to C
2.5.2 Migration from C to O or N
2.5.3 Migration from B to C or O
2.6 Two Multistep Reactions
2.6.1 The Swem Oxidation
2.6.2 The Mitsunobu Reaction
2.7 Summary
Problems
3 Polar Reactions Under Acidic Conditions
3.1 Carbocations
3.1.1 CarbOCation Stability
3.1.2 Carbocation Generation；The Role of Protonation
3.1.3 Typical Reactions of Carbocations；Rearrangements
3.2 Substitution and 一Elimination Reactions at C（sp3）一X
3.2.1 Substitution by the SNl and SN2 Mechanisms
3.2.2 Elimination by the E1 Mechanism
3.2.3 Predicting Substitution VS.Elimination
3.3 Electrophilic Addition to Nucleophilic C=C Bonds
3.4 Substitution atNucleophilic C=C Bonds
3.4.1 Electrophilic Aromatic Substitution
3.4.2 Aromatic Substitution of Anilines via Diazonium Salts
3.4.3 Electrophilic Aliphatic Substitution
3.5 Nucleophilic Addition to and Substitution at Electrophilic Bonds
3.5.1 Heteroatom Nucleophiles
3.5.2 Carbon Nucleophiles
3.6 Summary
Problems
4 Pericyclic Reactions
4.1 Introduction
4.1.1 Classes of Pericyclic Reactions
4.1.2 Polyene MOs
4.2 Electrocyclic Reactions
4.2.1 Typical Reactions
4.2.2 StereosF ecificily
4.2.3 Stereoselectivity
4.3 Cycloadditions
4.3.1 Typical Reactions
4.3.2 Regioselectivity
4.3.3 StereosF ecificity
4.3.4 Stereoselectivity
4.4 Sigmatropic Rearrangements
4.4. I Typical Reactions
4.4.2 Stereospecificily
4.4.3 Stereoselectivity
4.5 Ene Reactions
4.6 Summary
Problems
5 Free-Radical Reactions
5.1 Free Radicals
5.1.1 Stability
5.1.2 Generaticn from Closed-Shell Species
5.1.3 Typical Reacticns
5.1.4 Chain vs. Nonchain Mechanisms
5.2 Chain Free-Radical Reactions
5.2.1 Substitution Reactions
5.2.2 Addition and Fragmentation Reactions
5.3 Nonchain Free-Radical Reactions
5.3.1 Photochemical Reactions
5.3.2 Reductions and Oxidations with Metals
5.3.3 Cycloaromatizations
5.4 Miscellaneous Radical Reactions
5.4.1 1,2-Anionic Rearrangements; Lone-Pair Inversion
5.4.2 Triplet Carbenes and Nitrenes
5.5 Summary
Problems
6 Transition-Metal-Mediated and -Catalyzed Reactions
6.1 Introduction to the Chemistry of Transition Metals
6.1.1 Conventicns cf Drawing Structures
6.1.2 Counting Electrons
6.1.3 Typical Reactions
6.1.4 Stoichiometric vs. Catalytic Mechanisms
6.2 Addition Reactions
6.2.1 Late-Metal-Catalyzed Hydrogenation and Hydrometallation (Pd, Pt, Rh)
6.2.2 Hydroformylation (Co, Rh)
6.2.3 Hydrozirconation (Zr)
6.2.4 Alkene Polymerization (Ti, Zr, Sc, and others)
6.2.5 Cyclopropanation, Epoxidation, and Aziridination of Alkenes (Cu, Rh, Mn, Ti)
6.2.6 Dihydroxylation and Aminohydroxylation of Alkenes (Os)
6.2.7 Nucleophilic Addition to Alkenes and Alkynes (Hg, Pd)
6.2.8 Conjugate Addition Reactions (Cu)
6.2.9 Reducfive Coupling Reactions (Ti, Zr)
6.2.10 Pauson-Khand Reaction (Co)
6.2.11 D6tz Reaction (Cr)
6.2.12 Metal-Catalyzed Cycloaddition and Cyclotrimerizafion (Co, Ni, Rh)
6.3 Substitution Reactions
6.3.1 Hydrogenolysis (Pd)
6.3.2 Carbonylation of Alkyl Halides (Pd, Rh)
6.3.3 Heck Reaction (Pd)
6.3.4 Coupling Reactions Between Nucleophiles and C(spg)-x: Kumada, Stille, Suzuki, Negishi,Buchwald-Hartwig,
Sonogashira, and Ullmann Reactions (Ni, Pd, Cu)
6.3.5 Allylic Substitution (Pd)
6.3.6 Pd-Catalyzed Nucleophilic Substitution of Alkenes; Wacker Oxidation
6.3.7 Tebbe Reaction (Ti)
6.3.8 Propargyl Substitution in Co-Alkyne Complexes
6.4 Rearrangement Reactions
6.4.1 Alkene Isomerization (Rh)
6.4.2 Olefin and Alkyne Metathesis (Ru, W, Mo, Ti)
6.5 Elimination Reactions
6.5.1 Oxidation of Alcohols (Cr, Ru)
6.5.2 Decarbonylation of Aldehydes (Rh)
6.6 Summary
Problems
7 Mixed-Mechanism Problems
A Final Word
Index
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