Organic Synthesis

Chapter 1: Retrosynthesis, Stereochemistry, And Conformations

• • 1.1. Introduction
• • 1.2. The Disconnection Protocol
• • 1.3. Bond Proximity and Implications for Chemical Reactions
• • 1.4. Stereochemistry
• • 1.5. Conformations
• • 1.6. Conclusion

Chapter 2: Acids And Bases and Addition Reactions

• • 2.1. Introduction
• • 2.2. Brønsted-Lowry Acids and Bases
• • 2.3. Lewis Acids
• • 2.4 Hard-Soft Acid-Base Theory
• • 2.5. Acid-Base Reactions in Organic Chemistry
• • 2.5. Addition Reactions
• • 2.6. Conclusion

Chapter 3: Functional Group Exchange Reactions. Aliphatic and Aromatic Substitution, and Elimination Reactions

• • 3.1. Introduction
• • 3.2. Aliphatic Substitution Reactions
• • 3.3. Heteroatom-Stabilized Carbocations
• • 3.4. Substitution by Halogen
• • 3.5. Elimination Reactions
• • 3.6. Characteristics Of Substitution and Elimination Reactions
• • 3.7. Syn-Elimination Reactions
• • 3.8. 1,3-Elimination (Decarboxylation)
• • 3.9. 1,3-Elimination (Grob Fragmentation)
• • 3.10. Aromatic Substitution

Chapter 4: Acids, Bases, And Functional Group Exchange Reactions. Acyl Addition and Acyl Substitution

• • 4.1. Introduction
• • 4.2. Nucleophilic Acyl Addition and Substitution
• • 4.3. Conjugate Addition
• • 4.4. Functional Group Manipulation by Rearrangement
• • 4.5. Macrocyclic Compounds
• • 4.6. Conclusion

Chapter 5: Functional Groups Exchange Reactions. Protecting Groups

• • 5.1. Introduction
• • 5.2. When Are Protecting Groups Needed?
• • 5.3. Protecting Groups for Alcohols, Carbonyls, And Amines
• • 5.4. Conclusion

Chapter 6: Functional Group Exchange Reactions. Oxidations

• • 6.1. Introduction
• • 6.2. Alcohols To Carbonyls (CH-OH ® C=O)
• • 6.3. Formation of Phenols and Quinones
• • 6.4. Oxidation of Alkenes to Epoxides
• • 6.5. Conversion of Alkenes to Diols (C=C ® CHOH-CHOH)
• • 6.6. Baeyer-Villiger Oxidation (RCOR' ® RCO2R')
• • 6.7. Oxidative Bond Cleavage (C=C ® C=O + O=C)
• • 6.8. Oxidation Of Alkyl or Alkenyl Fragments (CH ® C=O or C—OH)
• • 6.9. Oxidation Of Sulfur, Selenium, And Nitrogen
• • 6.10. Conclusion

Chapter 7: Functional Group Exchange Reactions. Reductions

• • 7.1. Introduction
• • 7.2. The Nature of Hydride Reducing Agents
• • 7.3. Borane and Aluminum Hydride
• • 7.4. Sodium Borohydride
• • 7.5. Alternative Metal Borohydrides (Li, Zn, Ce)
• • 7.6. Lithium Aluminum Hydride
• • 7.7. Hydride Reducing Agents with Electron-Releasing Groups
• • 7.8. Hydride Reducing Agents with Electron-Withdrawing Groups
• • 7.9. Stereoselectivity In Reductions
• • 7.10. Catalytic Hydrogenation
• • 7.11. Dissolving Metal Reductions
• • 7.12. Nonmetallic Reducing Agents
• • 7.13. Conclusion

Chapter 8: SYNTHETIC STRATEGIES

• • 8.1. Introduction
• • 8.2. Target Selection
• • 8.3. Retrosynthesis
• • 8.4. Synthetic Strategies
• • 8.5. The Strategic Bond Approach
• • 8.6. Strategic Bonds in Rings
• • 8.7. Selected Synthetic Strategies: Ra current popular target
• • 8.8. Biomimetic Approach to Retrosynthesis
• • 8.9. The Chiral Template Approach
• • 8.10. Degradation Techniques as a Tool for Retrosynthesis
• • 8.11. Computer Generated Strategies
• • 8.12. Conclusion

Chapter 9: Functional Group Exchange Reactions. Hydroboration

• • 9.1. Introduction
• • 9.2. Preparation of Alkyl Boranes
• • 9.3. Preparation of Alkenylboranes
• • 9.4. Formation of Oxygen-Containing Functional Groups
• • 9.5. Other Functional Group Exchange Reactions
• • 9.6. Conclusion

Chapter 10: Functional Group Exchange Reactions. Selectivity

• • 10.1. Introduction
• • 10.2. Stereocontrol In Acyclic Systems
• • 10.3. Stereocontrol In Cyclic Systems
• • 10.4. Neighboring Group Effects and Chelation Effects
• • 10.5. Acyclic Stereocontrol Via Cyclic Precursors
• • 10.6. Baldwin's Rules for Ring Closure
• • 10.7. Conclusion

Chapter 11: Carbon-Carbon Bond-Forming Reactions. Cyanide, Alkyne Anions, Grignard Reagents, and Organolithium Reagents

• • 11.1. Introduction
• • 11.2. Cyanide
• • 11.3. Alkyne Anions (R-CºC:-)
• • 11.4 Grignard Reagents (C—Mg)
• • 11.5. Grignard Reagents. Reduction, Organocerium Reagents, and Enolization
• • 11.6. Organolithium Reagents (C—Li)
• • 11.7. Conclusion

Chapter 12: Carbon–Carbon Bond-Forming Reactions. Stabilized Carbanions, Organocuprates, and Ylids

• • 12.1. Introduction
• • 12.2. Sulfur Stabilized Carbanions and Umpolung
• • 12.3. Organocopper Reagents (C—Cu)
• • 12.4. Phenolic Carbanions
• • 12.5. Ylids
• • 12.6. Transition Metal Olefination Reagents
• • 12.7. Silane Reagents
• • 12.8. Conclusion

Chapter 13: Carbon-Carbon Bond-Forming Reactions. Enolate Anions

• • 13.1. Introduction
• • 13.2. Formation Of Enolate Anions
• • 13.3. Reactions Of Enolate Anions with Electrophiles
• • 13.4. Enolate Condensation Reactions
• • 13.5. Stereoselective Enolate Reactions
• • 13.6. Enamines
• • 13.7. Michael Addition and Related Reactions
• • 13.8. Enolate Reactions of a Halo Carbonyl Derivatives

Chapter 14: Pericyclic Reactions. The Diels–Alder Reaction

• • 14.1. Introduction
• • 14.2. Frontier Molecular Orbital Theory
• • 14.3. HOMO, LUMO Energies and Orbital Coefficients
• • 14.4. Allowed and Forbidden Reactions
• • 14.5. The Diels-Alder Reaction
• • 14.6. Rate Enhancement in Diels-Alder Reactions
• • 14.7. Intramolecular Diels-Alder Reactions
• • 14.8. Inverse Electron Demand and The Retro Diels-Alder Reactions
• • 14.9. Heteroatom Diels-Alder Reactions
• • 14.10. Enantioselective Diels-Alder Reactions
• • 14.11. Conclusion

Chapter 15: Pericyclic Reactions: [m+n]-Cycloadditions, Sigmatropic Rearrangements, Electrocyclic and Ene Reactions

• • 15.1. Introduction
• • 15.2. [2+2]-Cycloaddition Reactions
• • 15.3. Electrocyclic Reactions
• • 15.4. [3+2]-Cycloaddition Reactions
• • 15.5. (m+n]-Cycloaddition Reactions
• • 15.5. Sigmatropic Rearrangements
• • 15.6. The Ene Reaction
• • 15.7. Conclusion

Chapter 16: Carbon-Carbon Bond-Forming Reactions. Carbocation and Oxocarbenium Ion Intermediates

• • 16.1. Introduction
• • 16.2. Carbocations
• • 16.3. Carbocations and Carbon–Carbon Bond Forming Reactions
• • 16.4. Friedel-Crafts Reactions
• • 16.5. Friedel-Crafts Reactions: Formation of Heteroatom–Containing Derivatives
• • 16.6. Conclusion

Chapter 17: Formation Of Carbon-Carbon Bonds Via Radicals and Carbenes

• • 17.1. Introduction
• • 17.2. Structure Of Radicals
• • 17.3. Formation Of Radicals by Thermolysis
• • 17.4. Photochemical Formation of Radicals
• • 17.5. Reactions Of Free Radicals
• • 17.6. Intermolecular Radical Reactions
• • 17.7. Intramolecular Radical Reactions (Radical Cyclization)
• • 17.8. Metal-Induced Radical Reactions
• • 17.9. Carbenes And Carbenoids
• • 17.10. Conclusion

Chapter 18: Metal-Mediated, Carbon-Carbon Bond-Forming Reactions

• • 18.1. Introduction
• • 18.2. Copper-Catalyzed Coupling Reactions
• • 18.3. p-Allyl Palladium Complexes
• • 18.4. Named Palladium-Catalyzed Coupling Reactions
• • 18.5. p-Allyl Nickel Complexes
• • 18.6. Metathesis Reactions
• • 18.7. Pauson-Khand Reaction
• • 18.8. Organometallic Compounds as Carbanionic Reagents
• • 18.9. Electrophilic Iron Complexes
• • 18.10. Conclusion

Chapter 19: Combinatorial And Process Chemistry

• • 19.1. Combinatorial Chemistry
• • 19.2. Process Chemistry
• • 19.3. Continuous Flow Synthesis
• • 19.4. Conclusion