Advanced Organic Chemistry

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1 Advanced Organic Chemistry THIRD EDITION Part A: Structure and Mechanisms FRANCIS A. CAREY and RICHARD J. SUNDBERG University of Virginia Charlottesville, Virginia PLENUM PRESS NEW YORK AND LONDON

2 Contents of Part A Chapter 1. Chemical Bonding and Structure Valence Bond Approach to Chemical Bonding Bond Energies, Lengths, and Dipoles Molecular Orbital Theory and Methods Qualitative Application of Molecular Orbital Theory Hückel Molecular Orbital Theory Perturbation Molecular Orbital Theory Interactions between u and TT Systems Hyperconjugation General References 59 Problems 59 Chapter 2. Stereochemical Principles Enantiomeric Relationships Diastereomeric Relationships Stereochemistry of Dynamic Processes Prochiral Relationships 98 General References 108 Problems 108 Chapter 3. Conformational, Steric, and Stereoelectronic Effects Steric Strain and Molecular Mechanics Conformations of Acyclic Molecules Conformations of Cyclohexane Derivatives Carbocyclic Rings Other Than Six-Membered 141 vn

3 VÜi 3.5. The Effect of Heteroatoms on Conformational Equilibria Molecular Orbital Methods Applied to Conformational Analysis. 151 CONTENTS OF rr j PART A 3.7. Conformational Effects on Reactivity Angle Strain and Its Effect on Reactivity Relationships between Ring Size and Facility of Ring Closure Torsional and Stereoelectronic Effects on Reactivity 167 General References 172 Problems 172 Chapter 4. Study and Description of Organic Reaction Mechanisms Thermodynamic Data 180 <*.2. Kinetic Data Substituent Effects and Linear Free-Energy Relationships Basic Mechanistic Concepts: Kinetic versus Thermodynamic Control, Hammond's Postulate, and the Curtin-Hammett Principle Kinetic versus Thermodynamic Control Hammond's Postulate The Curtin-Hammett Principle Isotope Effects Isotopes in Labeling Experiments Characterization of Reaction Intermediates Catalysis by Acids and Bases Lewis Acid Catalysis 229,4.10. Solvent Effects Structural Effects in the Gas Phase Stereochemistry Conclusion 244 General References 244 Problems 245 Chapter 5. Nucleophilic Substitution The Limiting Cases Substitution by the Ionization (S N 1) Mechanism The Limiting Cases Substitution by the Direct Displacement (S N 2) Mechanism Detailed Mechanistic Description and Borderline Mechanisms Carbocations Nucleophilicity and Solvent Effects LeaVing Group Effects Steric and Strain Effects on Substitution and Ionization Rates Substituent Effects on Reactivity Stereochemistry of Nucleophilic Substitution 297

4 5.10. Neighboring-Group Participation 305 ix Rearrangements of Carbocations 313 CONTENTS OF The Norbornyl Cation and Other Nonclassical Carbocations PART A General References 328 Problems 328 Chapter 6. Polar Addition and Elimination Reactions Addition of Hydrogen Halides to Alkenes Acid-Catalyzed Hydration and Related Addition Reactions Addition of Halogens Electrophilic Additions Involving Metal Ions Additions to Alkynes and Allenes The E2, El, and Elcb Mechanisms Orientation Effects in Elimination Reactions Stereochemistry of E2 Elimination Reactions Dehydration of Alcohols Eliminations Not Involving C H Bonds 384 General References 389 Problems 389 Chapter 7. Carbanions and Other Nucleophilic Carbon Species Acidity of Hydrocarbons Carbanions Stabilized by Functional Groups Enols and Enamines Carbanions as Nucleophiles in S N 2 Reactions 423 General References 430 Problems 431 Chapter 8. Reactions of Carbonyl Compounds Hydration and Addition of Alcohols to Aldehydes and Ketones Addition-Elimination Reactions of Aldehydes and Ketones Addition of Carbon Nucleophiles to Carbonyl Groups Reactivity of Carbonyl Compounds toward Addition Ester Hydrolysis Aminolysis of Esters Amide Hydrolysis Acylation of Nucleophilic Oxygen and Nitrogen Groups Intramolecular Catalysis 479 General References 487 Problems 487

5 X Chapter 9. Aromaticity 499 CONTENTS OF PART A 9.1. The Concept ol Aromaticity The Annulenes Aromaticity in Charged Rings Homoaromaticity Fused-Ring Systems Heterocyclic Rings 531 General References 532 Problems 532 Chapter 10. Aromatic Substitution Electrophilic Aromatic Substitution Reactions Structure-Reactivity Relationships Reactivity of Polycyclic and Heteroaromatic Compounds Specific Substitution Mechanisms Nitration Halogenation Protonation and Hydrogen Exchange Friedel-Crafts Alkylation and Related Reactions Friedel-Crafts Acylation and Related Reactions Coupling with Diazonium Compounds Substitution of Groups Other than Hydrogen Nucleophilic Aromatic Substitution by Addition-Elimination Nucleophilic Aromatic Substitiution by the Elimination-Addition Mechanism 583 General References 587 Problems 587 Chapter 11. Concerted Reactions Electrocyclic Reactions Sigmatropic Rearrangements Cycloaddition Reactions 625 General References 640 Problems 640 Chapter 12. Free-Radical Reactions Generation and Characterization of Free Radicals Background 651

6 Stable and Persistent Free Radicals 652 xi Direct Detection of Radical Intermediates 655 CONTENTS OF Sources of Free Radicals 660 PART A Structural and Stereochemical Properties of Radical Intermediates Charged Radical Species Characteristics of Reaction Mechanisms Involving Radical Intermediates Kinetic Characteristics of Chain Reactions Structure-Reactivity Relationships Free-Radical Substitution Reactions Halogenation Oxidation Free-Radical Addition Reactions Addition of Hydrogen Halides Addition of Halomethanes Addition of Other Carbon Radicals Addition of Thiols and Thiocarboxylic Acids Intramolecular Free-Radical Reactions Rearrangement and Fragmentation Reactions of Free Radicals Rearrangement Reactions Fragmentation Reactions Electron Transfer Reactions Involving Transition Metal Ions S RN 1 Substitution Processes 712 General References. 719 Problems 719 Chapter 13. Photochemistry General Principles Orbital Symmetry Considerations Related to Photochemical Reactions Photochemistry of Carbonyl Compounds Photochemistry of Alkenes and Dienes Photochemistry of Aromatic Compounds 762 General References 764 Problems 765 References for Problems 773 Index 787

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