March's Advanced Organic Chemistry

Chapter 1: Localized Chemical Bonding

• • 1.A. Covalent Bonding
• • 1.B. Multiple Valence
• • 1.C. Hybridization
• • 1.D. Multiple Bonds
• • 1.E. Photoelectron Spectroscopy
• • 1.F. Electronic Structures of Molecules
• • 1.G. Electronegativity
• • 1.H. Dipole Moment
• • 1.I. Inductive and Field Effects
• • 1.J. Bond Distances
• • 1.K. Bond Angles
• • 1.L. Bond Energies

Chapter 2: Delocalized Chemical Bonding

• • 2.A. Molecular Orbitals
• • 2.B. Bond Energies and Distances in Compounds Containing Delocalized Bonds
• • 2.C. Molecules that have Delocalized Bonds
• • 2.D. Cross-Conjugation
• • 2.E. The Rules of Resonance
• • 2.F. The Resonance Effect
• • 2.G. Steric Inhibition of Resonance and the Influences of Strain
• • 2.H. pπ–dπ Bonding. Ylids
• • 2.I. Aromaticity
• • 2.I.i. Six-Membered Rings
• • 2.I.ii. Five-, Seven-, and Eight-Membered Rings
• • 2.I.iii. Other Systems Containing Aromatic Sextets
• • 2.J. Alternant and Nonalternant Hydrocarbons
• • 2.K. Aromatic Systems with Electron Numbers other than Six
• • 2.K.i. Systems of Two Electrons
• • 2.K.ii. Systems of Four Electrons: Antiaromaticity
• • 2.K.iii. Systems of Eight Electrons
• • 2.K.iv. Systems of Ten Electrons
• • 2.K.v. Systems of More than Ten Electrons: 4n + 2 Electrons
• • 2.K.vi. Systems of More than Ten Electrons: 4n Electrons
• • 2.L. Other Aromatic Compounds
• • 2.M. Hyperconjugation
• • 2.N. Tautomerism
• • 2.N.i. Keto-Enol Tautomerism
• • 2.N.ii. Other Proton-Shift Tautomerism

Chapter 3: Bonding Weaker Than Covalent

• • 3.A. Hydrogen Bonding
• • 3.B. π–π Interactions
• • 3.C. Addition Compounds
• • 3.C.i. Electron Donor–Acceptor Complexes
• • 3.C.ii. Crown Ether Complexes and Cryptates
• • 3.C.iii. Inclusion Compounds
• • 3.C.iv. Cyclodextrins
• • 3.D. Catenanes and Rotaxanes
• • 3.E. Cucurbit[n]Uril-Based Gyroscane

Chapter 4: Stereochemistry and Conformation

• • 4.A. Optical Activity and Chirality
• • 4.B. Dependence of Rotation on Conditions of Measurement
• • 4.C. What kinds of Molecules Display Optical Activity?
• • 4.D. The Fischer Projection
• • 4.E. Absolute Configuration
• • 4.E.i. The Cahn–Ingold–Prelog System
• • 4.E.ii. Methods of Determining Configuration
• • 4.F. Optical Purity
• • 4.G. The Cause of Optical Activity
• • 4.H. Molecules with more than One Stereogenic Center
• • 4.I. Asymmetric Synthesis
• • 4.J. Methods of Resolution
• • 4.K. Cis–Trans Isomerism
• • 4.K.i. Cis–Trans Isomerism Resulting from Double Bonds
• • 4.K.ii. Cis–Trans Isomerism of Monocyclic Compounds
• • 4.K.iii. Cis–Trans Isomerism of Fused and Bridged Ring Systems
• • 4.L. Out–In Isomerism
• • 4.M. Enantiotopic and Diastereotopic Atoms, Groups, and Faces
• • 4.N. Stereospecific and Stereoselective Syntheses
• • 4.O. Conformational Analysis
• • 4.O.i. Conformation in Open-Chain Systems
• • 4.O.ii. Conformation in Six-Membered Rings
• • 4.O.iii. Conformation in Six-Membered Rings Containing Heteroatoms
• • 4.O.iv. Conformation in Other Rings
• • 4.P. Molecular Mechanics
• • 4.Q. Strain
• • 4.Q.i. Strain in Small Rings
• • 4.Q.ii. Strain in Other Rings
• • 4.Q.iii. Unsaturated Rings
• • 4.Q.iv. Strain Due to Unavoidable Crowding

Chapter 5: Carbocations, Carbanions, Free Radicals, Carbenes, and Nitrenes

• • 5.A. Carbocations
• • 5.A.i. Nomenclature
• • 5.A.ii. Stability and Structure of Carbocations
• • 5.A.iii. The Generation and Fate of Carbocations
• • 5.B. Carbanions
• • 5.B.i. Stability and Structure
• • 5.B.ii. The Structure of Grignard Reagents and Organolithium Reagents
• • 5.B.iii. The Generation and Fate of Carbanions
• • 5.C. Free Radicals
• • 5.C.i. Stability and Structure
• • 5.C.ii. The Generation and Fate of Free Radicals
• • 5.C.iii. Radical Ions
• • 5.D. Carbenes
• • 5.D.i. Stability and Structure
• • 5.D.ii. The Generation and Fate of Carbenes
• • 5.D.iii. N-Heterocyclic Carbenes
• • 5.E. Nitrenes

Chapter 6: Mechanisms and Methods of Determining Them

• • 6.A. Types of Mechanism
• • 6.B. Types of Reaction
• • 6.C. Thermodynamic Requirements for Reaction
• • 6.D. Kinetic Requirements for Reaction
• • 6.E. The Baldwin Rules for Ring Closure
• • 6.F. Kinetic and Thermodynamic Control
• • 6.G. The Hammond Postulate
• • 6.H. Microscopic Reversibility
• • 6.I. Marcus Theory
• • 6.J. Methods of Determining Mechanisms
• • 6.J.i. Identification of Products
• • 6.J.ii. Determination of the Presence of an Intermediate
• • 6.J.iii. The Study of Catalysis
• • 6.J.iv. Isotopic Labeling
• • 6.J.v. Stereochemical Evidence
• • 6.J.vi. Kinetic Evidence
• • 6.J.vii. Isotope Effects
• • 6.K. Catalyst Development

Chapter 7: Irradiation Processes and Techniques that Influence Reactions in Organic Chemistry

• • 7.A. Photochemistry
• • 7.A.i. Excited States and the Ground State
• • 7.A.ii. Singlet and Triplet States: “Forbidden” Transitions
• • 7.A.iii. Types of Excitation
• • 7.A.iv. Nomenclature and Properties of Excited States
• • 7.A.v. Photolytic Cleavage
• • 7.A.vi. The Fate of the Excited Molecule: Physical Processes
• • 7.A.vii. The Fate of the Excited Molecule: Chemical Processes
• • 7.A.viii. The Determination of Photochemical Mechanisms
• • 7.B. Sonochemistry
• • 7.C. Microwave Chemistry
• • 7.D. Flow Chemistry
• • 7.E. Mechanochemistry

Chapter 8: Acids and Bases

• • 8.A. Brønsted Theory
• • 8.A.i. Brønsted Acids
• • 8.A.ii. Brønsted Bases
• • 8.B. The Mechanism of Proton Transfer Reactions
• • 8.C. Measurements of Solvent Acidity
• • 8.D. Acid and Base Catalysis
• • 8.E. Lewis Acids and Bases
• • 8.E.i. Hard–Soft Acids–Bases
• • 8.F. The Effects of Structure on the Strengths of Acids and Bases
• • 8.G. The Effects of the Medium on Acid and Base Strength

Chapter 9: Effects of Structure and Medium on Reactivity

• • 9.A. Resonance and Field Effects
• • 9.B. Steric Effects
• • 9.C. Quantitative Treatments of the Effect of Structure on Reactivity
• • 9.D. Effect of Medium on Reactivity and Rate
• • 9.E. High Pressure
• • 9.F. Water and other Nonorganic Solvents
• • 9.G. Ionic Liquid Solvents
• • 9.H. Solventless Reactions

Chapter 10: Aliphatic Substitution: Nucleophilic and Organometallic

• • 10.A. Mechanisms
• • 10.A.i. The SN2 Mechanism
• • 10.A.ii. The SN1 Mechanism
• • 10.A.iii. Ion Pairs in the SN1 Mechanism
• • 10.A.iv. Mixed SN1 and SN2 Mechanisms
• • 10.B. Set Mechanisms
• • 10.C. The Neighboring-Group Mechanism
• • 10.C.i. Neighboring-Group Participation by π and σ Bonds: Nonclassical Carbocations
• • 10.D. The SNi Mechanism
• • 10.E. Nucleophilic Substitution at an Allylic Carbon: Allylic Rearrangements
• • 10.F. Nucleophilic Substitution at an Aliphatic Trigonal Carbon: The Tetrahedral Mechanism
• • 10.G. Reactivity
• • 10.G.i. The Effect of Substrate Structure
• • 10.G.ii. The Effect of the Attacking Nucleophile
• • 10.G.iii. The Effect of the Leaving Group
• • 10.G.iv. The Effect of the Reaction Medium
• • 10.G.v. Phase-Transfer Catalysis
• • 10.G.vi. Influencing Reactivity by External Means
• • 10.G.vii. Ambident (Bidentant) Nucleophiles: Regioselectivity
• • 10.G.viii. Ambident Substrates
• • 10.H. Reactions

Chapter 11: Aromatic Substitution: Electrophilic

• • 11.A. Mechanisms
• • 11.A.i. The Arenium Ion Mechanism
• • 11.B. Orientation and Reactivity
• • 11.B.i. Orientation and Reactivity in Monosubstituted Benzene Rings
• • 11.B.ii. The Ortho/Para Ratio
• • 11.B.iii. Ipso Attack
• • 11.B.iv. Orientation in Benzene Rings with more than one Substituent
• • 11.B.v. Orientation in Other Ring Systems
• • 11.C. Quantitative Treatments of Reactivity in the Substrate
• • 11.D. A Quantitative Treatment of Reactivity of the Electrophile: The Selectivity Relationship
• • 11.E. The Effect of the Leaving Group
• • 11.F. Reactions

Chapter 12: Aliphatic, Alkenyl, and Alkynyl Substitution: Electrophilic and Organometallic

• • 12.A. Mechanisms
• • 12.A.i. Bimolecular Mechanisms: SE2 and SEi
• • 12.A.ii. The SE1 Mechanism
• • 12.A.iii. Electrophilic Substitution Accompanied by Double-Bond Shifts
• • 12.A.iv. Other Mechanisms
• • 12.B. Reactivity
• • 12.C. Reactions

Chapter 13: Aromatic Substitution: Nucleophilic and Organometallic

• • 13.A. Mechanisms
• • 13.A.i. The SNAr Mechanism
• • 13.A.ii. The SN1 Mechanism
• • 13.A.iii. The Benzyne Mechanism
• • 13.A.iv. The SRN1 Mechanism
• • 13.A.v. Other Mechanisms
• • 13.B. Reactivity
• • 13.B.i. The Effect of Substrate Structure
• • 13.B.ii. The Effect of the Leaving Group
• • 13.B.iii. The Effect of the Attacking Nucleophile
• • 13.C. Reactions

Chapter 14: Radical Reactions

• • 14.A. Mechanisms
• • 14.A.i. Radical Mechanisms in General
• • 14.A.ii. Free-Radical Substitution Mechanisms
• • 14.A.iii. Mechanisms at an Aromatic Substrate
• • 14.A.iv. Neighboring-Group Assistance in Free-Radical Reactions
• • 14.B. Reactivity
• • 14.B.i. Reactivity for Aliphatic Substrates
• • 14.B.ii. Reactivity at a Bridgehead
• • 14.B.iii. Reactivity in Aromatic Substrates
• • 14.B.iv. Reactivity in the Attacking Radical
• • 14.B.v. The Effect of Solvent on Reactivity
• • 14.C. Reactions

Chapter 15: Addition to Carbon–Carbon Multiple Bonds

• • 15.A. Mechanisms
• • 15.A.i. Electrophilic Addition
• • 15.A.ii. Nucleophilic Addition
• • 15.A.iii. Free-Radical Addition
• • 15.A.iv. Cyclic Mechanisms
• • 15.A.v. Addition to Conjugated Systems
• • 15.B. Orientation and Reactivity
• • 15.B.i. Reactivity
• • 15.B.ii. Orientation
• • 15.B.iii. Stereochemical Orientation
• • 15.B.iv. Addition to Cyclopropane Rings
• • 15.C. Reactions

Chapter 16: Addition to Carbon–Heteroatom Multiple Bonds

• • 16.A. Mechanism and Reactivity
• • 16.A.i. Nucleophilic Substitution at an Aliphatic Trigonal Carbon: The Tetrahedral Mechanism
• • 16.B. Reactions

Chapter 17: Elimination Reactions

• • 17.A. Mechanisms and Orientation
• • 17.A.i. The E2 Mechanism
• • 17.A.ii. The E1 Mechanism
• • 17.A.iii. The E1cB Mechanism
• • 17.A.iv. The E1–E2–E1cB Spectrum
• • 17.A.v. The E2C Mechanism
• • 17.B. Regiochemistry of the Double Bond
• • 17.C. Stereochemistry of the Double Bond
• • 17.D. Reactivity
• • 17.D.i. Effect of Substrate Structure
• • 17.D.ii. Effect of the Attacking Base
• • 17.D.iii. Influence of the Leaving Group
• • 17.D.iv. Influence of the Medium
• • 17.E. Mechanisms and Orientation in Pyrolytic Eliminations
• • 17.E.i. Mechanisms
• • 17.E.ii. Orientation in Pyrolytic Eliminations
• • 17.F. Reactions

Chapter 18: Rearrangements

• • 18.A. Mechanisms
• • 18.A.i. Nucleophilic Rearrangements
• • 18.A.ii. The Actual Nature of the Migration
• • 18.A.iii. Migratory Aptitudes
• • 18.A.iv. Memory Effects
• • 18.B. Longer Nucleophilic Rearrangements
• • 18.C. Free-Radical Rearrangements
• • 18.D. Carbene Rearrangements
• • 18.E. Electrophilic Rearrangements
• • 18.F. Reactions

Chapter 19: Oxidations and Reductions

• • 19.A. Mechanisms
• • 19.B. Reactions
• • 19.B.i. Oxidations
• • 19.B.ii. Reductions

Chapter APPENDIX A: THE LITERATURE OF ORGANIC CHEMISTRY