March's Advanced Organic Chemistry: Reactions, Mechanisms, and Structure -- Contents -- Preface -- Common Abbreviations -- Biographical Statement -- Part I: Introduction -- 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 -- 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 10 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 -- 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 -- 4. Stereochemistry and Conformation -- 4.A. Optical Activity and Chirality -- 4.A.i. Dependence of Rotation on Conditions of Measurement -- 4.B. What Kinds of Molecules Display Optical Activity? -- 4.C. The Fischer Projection -- 4.D. Absolute Configuration -- 4.D.i. The CAHN-INGOLD-PRELOG System -- 4.D.ii. Methods of Determining Configuration -- 4.E. The Cause of Optical Activity -- 4.F. Molecules with more than One Stereogenic Center -- 4.G. Asymmetric Synthesis -- 4.H. Methods of Resolution -- 4.I. Optical Purity -- 4.J. cis-trans Isomerism -- 4.J.i. cis-trans Isomerism Resulting from Double Bonds -- 4.J.ii. cis-trans Isomerism of Monocyclic Compounds -- 4.J.iii. cis-trans Isomerism of Fused and Bridged Ring Systems -- 4.K. Out-In Isomerism -- 4.L. Enantiotopic and Diastereotopic Atoms, Groups, and Faces -- 4.M. Stereospecific and Stereoselective Syntheses -- 4.N. Conformational Analysis -- 4.N.i. Conformation in Open-Chain Systems -- 4.N.ii. Conformation in Six-Membered Rings -- 4.N.iii. Conformation in Six-Membered Rings Containing Heteroatoms -- 4.N.iv. Conformation in Other Rings -- 4.O. Molecular Mechanics -- 4.P. STRAIN -- 4.P.i. Strain in Small Rings -- 4.P.ii. Strain in Other Rings -- 4.P.iii. Unsaturated Rings -- 4.P.iv. Strain Due to Unavoidable Crowding -- 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 Organometallic Compounds -- 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.E. Nitrenes -- 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 -- 7. Irradiation Processes 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 -- 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 -- 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.D.i. High Pressure -- 9.D.ii. Water and Other Non-Organic Solvents -- 9.D.iii. Ionic Solvents -- 9.D.iv. Solventless Reactions -- Part II: Introduction -- 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 -- 10.H.i. Oxygen Nucleophiles -- 10.H.ii. Attack by OR at an Alkyl Carbon -- 10.H.iii. Sulfur Nucleophiles -- 10.H.iv. Nitrogen Nucleophiles -- 10.H.v. Halogen Nucleophiles -- 10.H.vi. Carbon Nucleophiles -- 11. Aromatic Substitution, Electrophilic -- 11.A. Mechanisms -- 11.A.i. The Arenium Ion Mechanism -- 11.A.ii. The SE1 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 -- 11.F.i. Hydrogen as the Leaving Group in Simple Substitution Reactions -- 11.F.ii. Hydrogen as the Leaving Group in Rearrangement Reactions -- 11.F.iii. Other Leaving Groups -- 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 -- 12.C.i. Hydrogen as Leaving Group -- 12.C.ii. Metals as Leaving Groups -- 12.C.iii. Halogen as Leaving Group -- 12.C.iv. Carbon Leaving Groups -- 12.C.v. Electrophilic Substitution at Nitrogen -- 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 -- 13.C.i. All Leaving Groups Except Hydrogen and N2+ -- 13.C.ii. Hydrogen as Leaving Group -- 13.C.iii. Nitrogen as Leaving Group -- 13.C.iv. Rearrangements -- 14. Substitution Reactions: Radical -- 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.