The Art of Writing Reasonable Organic Reaction Mechanisms

Table of Contents (3rd edition)

Chapter 1. The Basics.

1. Structure and Stability of Organic Compounds
   • Conventions of Drawing Structures; Grossman's Rule
   • Lewis Structures; Resonance Structures
   • Molecular Shape; Hybridization
   • Aromaticity
2. Bronsted Acidity and Basicity
   • pK_a Values
   • Tautomerism
3. Kinetics and Thermodynamics
4. Getting Started at Drawing a Mechanism
   • Reading and Balancing Organic Reaction Equations
   • Determining Which Bonds Are Made and Broken in a Reaction
5. Classes of Overall Transformations
6. Classes of Mechanisms
   • Polar Mechanisms
     • Nucleophiles
     • Electrophiles and Leaving Groups
     • Acidic and Basic Conditions; The pK_a Rule
     • A Typical Polar Mechanism
   • Free-Radical Mechanisms
   • Pericyclic Mechanisms
   • Transition-Metal-Catalyzed and -Mediated Mechanisms
7. Summary

Chapter 2. Polar Reactions under Basic Conditions.

1. Introduction to Substitution and Elimination
   • Substitution by the S_N2 Mechanism
   • β-Elimination by the E2 and E1cb Mechanisms
   • Predicting Substitution vs. Elimination
2. Addition of Nucleophiles to Electrophilic π Bonds
   • Addition to Carbonyl Compounds
   • Conjugate Addition; The Michael Reaction
3. Substitution at C(sp²)–X σ Bonds
   • Substitution at Carbonyl C
   • Substitution at Alkenyl and Aryl C
   • Metal Insertion, Halogen–Metal Exchange
4. Substitution and Elimination at C(sp³)–X σ Bonds, Part II
   • Substitution by the S_RN1 Mechanism
   • Substitution by the Elimination–Addition Mechanism
   • Substitution by the One-Electron Transfer Mechanism
   • Metal Insertion; Halogen–Metal Exchange
   • α-Elimination; Generation and Reactions of Carbenes
5. Base-Promoted Rearrangements
   • Migrations from C to C
   • Migrations from C to O
   • Migrations from C to N
   • Migrations from B to C or O
6. Two Multistep Reactions
   • Swern Oxidation
   • Mitsunobu Reaction
7. Summary

Chapter 3. Polar Reactions under Acidic Conditions.

1. Carbocations
   • Carbocation Stability
   • Carbocation Generation; The Role of Protonation
   • Typical Reactionsof Carbocations; Rearrangements
2. Substitution and β-Elimination Reactions at C(sp³)–X
   • Substitution by the S_N1 and S_N2 Mechanisms
   • Elimination by the E1 Mechanism
   • Predicting Substitution vs. Elimination
3. Electrophilic Addition to Nucleophilic C=C π Bonds
4. Substitution at Nucleophilic C=C π Bonds
   • Electrophilic Aromatic Substitution
   • Diazonium Ions
   • Electrophilic Aliphatic Substitution
5. Nucleophilic Addition to and Substitution at Electrophilic π Bonds.
   • Heteroatom Nucleophiles
   • Carbon Nucleophiles
6. Catalysis Involving Iminium Ions.
7. Summary

Chapter 4. Pericyclic Reactions.

1. Introduction
   • Classes of Pericyclic Reactions; Nomenclature
   • Polyene MOs
2. Electrocyclic Reactions
   • Typical Reactions
   • Stereospecificity (Woodward–Hoffmann Rules)
   • Stereoselectivity (Torquoselectivity)
3. Cycloadditions
   • Typical Reactions
     • The Diels–Alder Reaction
     • Other Cycloadditions
   • Regioselectivity (ortho–para Rule)
   • Stereospecificity (Woodward–Hoffmann Rules)
   • Stereoselectivity (endo Rule)
4. Sigmatropic Rearrangements
   • Typical Reactions
   • Stereospecificity (Woodward–Hoffmann Rules)
   • Stereoselectivity
5. Ene Reactions.
6. Summary

Chapter 5. Free Radical Reactions.

1. Free Radicals
   • Stability
   • Generation from Closed-Shell Species
   • Typical Reactions
   • Chain vs. Nonchain Mechanisms
2. Chain Free-Radical Reactions
   • Substitution Reactions
   • Addition and Fragmentation Reactions
3. Nonchain Free-Radical Reactions
   • Photochemical Reactions
   • Reductions and Oxidations with Metals
   • Cycloaromatizations
4. Miscellaneous Radical Reactions
   • 1,2-Anionic Rearrangements; Lone-Pair Inversion
   • Triplet Carbenes and Nitrenes
5. Summary

Chapter 6. Transition-Metal-Mediated and -Catalyzed Reactions.

1. Introduction to the Chemistry of Transition Metals
   • Conventions of Drawing Structures
   • Counting Electrons
     • Typical Ligands; Total Electron Count
     • Oxidation State and d Electron Count
   • Typical Reactions
   • Stoichiometric vs. Catalytic Mechanisms
2. 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)
   • Dötz Reaction (Cr)
   • Metal-Catalyzed Cycloaddition and Cyclotrimerization (Co, Ni, Rh)
3. Substitution Reactions
   • Hydrogenolysis (Pd)
   • Carbonylation of Alkyl Halides (Pd, Rh)
   • Heck Reaction (Pd)
   • Coupling Reactions between Nucleophiles and C(sp²)–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
   • C–H Activation Reactions (Pd, Ru, Rh)
   • Tebbe Reaction (Ti)
   • Propargyl Substitution in Co–Alkyne Complexes
4. Rearrangement Reactions
   • Alkene Isomerization (Rh)
   • Olefin and Alkyne Metathesis (Ru, W, Mo, Ti)
5. Elimination Reactions
   • Oxidation of Alcohols (Cr, Ru)
   • Decarbonylation of Aldehydes (Rh)
6. Summary

Chapter 7. Mixed Mechanism Problems.