Modern Synthesis Processes and Reactivity of Fluorinated Compounds

Chapter One. The Cosmic Origin of Fluorine: An Astronomer's View on Fluorine Synthesis

• 1. The Cosmic Origin of the Elements
• 2. The Cosmic Origin of Fluorine

Chapter Two. The Fluorine Atom in Health Care and Agrochemical Applications: A Contribution to Life Science

• 1. Introduction
• 2. Methods to Introduce Fluorine Into Organic Molecules
• 3. Use of Trifluoromethyl Group in Pharmaceuticals and Agrochemistry
• 4. Use of Difluoromethyl Group in Pharmaceuticals and Agrochemistry

3. Industrial Syntheses of Hydrohaloolefins and Related Products

• 1. Introduction
• 2. Hydrofluoroolefins
• 3. Other Hydrofluoroolefins
• 4. Hydrochlorofluoroolefins
• 5. Conclusion

4. Electrochemical Fluorination: A Powerful Tool for the Preparation of Organofluorine Compounds

• 1. Introduction and Historical Overview
• 2. Technical Aspects of the Electrochemical Fluorination (Simons Process)
• 3. Mechanism of Electrochemical Fluorination (Simons Process)
• 4. Carbon Chain Isomerization During Electrochemical Fluorination (Simons Process)
• 5. Electrochemical Fluorination of the Elementorganic Compounds

5. Once Upon a Time Was the Langlois' Reagent: A “Sleeping Beauty”

• 1. Introduction
• 2. Origin of the Trifluoromethanesulfinate Salts and Their First Uses
• 3. Rebirth of the “Langlois' Reagent”
• 4. Conclusions

6. Toward CF₃S Group: From Trifluoromethylation of Sulfides to Direct Trifluoromethylthiolation

• 1. Introduction
• 2. Indirect Methods
• 3. Direct Preparation: Trifluoromethylthiolation
• 4. Conclusions

7. Nucleophilic Di- and Trifluoromethylation of CO and CN Bonds

• 1. Introduction
• 2. Trifluoromethylation Reactions
• 3. Difluoromethylation Reactions
• 4. Conclusion

8. Oxidative Trifluoromethylation and Trifluoromethylthiolation

• 1. Introduction
• 2. Oxidative Trifluoromethylation
• 3. Oxidative Trifluoromethylthiolation
• 4. Other Oxidative Fluoroalkylations
• 5. Conclusion

9. Catalytic Enantioselective Fluorination

• 1. Introduction
• 2. Electrophilic Fluorination Methods
• 3. Nucleophilic Fluorination
• 4. Conclusions and Outlook

10. Development of Electrophilic Trifluoromethylating Reagents

• 1. Introduction
• 2. Historical Background
• 3. Electrophilic Trifluoromethylating Reagents
• 4. Conclusion

11. New Nucleophilic Fluoroalkylations

• 1. Introduction
• 2. Nucleophilic Trifluoroalkylation Reactions
• 3. Difluoroalkylation Reactions
• 4. Nucleophilic Monofluoroalkylation Reactions

12. Continuous Flow Selective Direct Fluorination Using Fluorine Gas

• 1. Introduction
• 2. Continuous Flow Processes Using Fluorine Gas
• 3. Selective Direct Fluorination by Continuous Flow Processes
• 4. Conclusions

13. Synthesis of Fluorinated Nitrogen-Containing Compounds Through Superelectrophilic Activation in Superacid HF/SbF₅

• 1. Introduction
• 2. Hydrofluorination of CC Double Bond in Superacid HF/SbF₅
• 3. Hydrofluorination of CC Triple Bond in Superacid HF/SbF₅
• 4. Cyclization and Cyclization/Fluorination in Superacid HF/SbF₅
• 5. Halofluorination of Unsaturated Nitrogen-Containing Substrates in Superacid HF/SbF₅
• 6. Exploitation of Superacid-Catalyzed Hydrofluorination of Unsaturated Amines in Superacid HF/SbF₅ for Bioorganic Studies
• 7. Conclusion

14. Visible Light–Induced (Per)fluoroalkylation by Photoredox Catalysis

• 1. Introduction
• 2. (Per)fluoroalkylation Reactions Using Photoredox-Induced Monofunctionalization
• 3. (Per)fluoroalkylation Using Photoredox-Induced Difunctionalization of Unsaturated Systems
• 4. Conclusion

15. Synthesis of Side Chain Fluorinated Amino Acids and Their Effects on the Properties of Peptides and Proteins

• 1. Introduction
• 2. Synthesis of Fluorinated Aliphatic α-Amino Acids
• 3. Fluorinated Amino Acids in Peptides
• 4. Summary and Prospects

16. Ionic Liquids and Polymers for Battery and Fuel Cells

• 1. Introduction
• 2. Fluorinated Compounds in Lithium-Ion Battery
• 3. Aromatic Ionomers Bearing Perfluorosulfonic Acid Side Chains

17. Strategic Incorporation of Fluorine for Drug Discovery and Development

• 1. Introduction
• 2. Case Study 1: Incorporation of Fluorine Increased the Binding Affinity of a Drug to Its Protein Target
• 3. Case Study 2: Incorporation of Fluorine Increased Potency In Vitro
• 4. Case Study 3: Incorporation of Fluorine Increased Both In Vitro and In Vivo Potency
• 5. Case Study 4: Use of a ¹⁸F-Positron Emission Tomographic Tracer Replaced an Expensive ¹¹C-Positron Emission Tomographic Tracer for Practical Diagnosis of Alzheimer Disease
• 6. Conclusions

18. Telomerization Reaction of 3,3,3-Trifluoropropene

• 1. Introduction
• 2. Telomerization of 3,3,3-Trifluoropropene
• 3. Synthesis of Surfactants Based on 3,3,3-Trifluoropropene
• 4. Conclusions

19. High Oxidation States in Transition Metal Fluorides

• 1. Introduction
• 2. 3d Elements
• 3. 4d Metals
• 4. 5d Elements
• 5. Outlook

20. Photochemical Syntheses of Fluorides in Liquid Anhydrous Hydrogen Fluoride

• 1. Introduction
• 2. Requirements of Photochemical Syntheses With Elemental F₂ in Anhydrous HF
• 3. Reaction Mechanism
• 4. Examples of F₂ Fluorinations in Liquid Anhydrous HF at Ambient Temperature
• 5. Conclusions

21. Sol–Gel Synthesis of Metal Fluorides: Reactivity and Mechanisms

• 1. Introduction
• 2. The Principle Chemistry of the Fluorolytic Sol–Gel Synthesis
• 3. Mechanistic Aspects of Fluorolytic Sol–Gel Synthesis as Seen by Nuclear Magnetic Resonance Methods
• 4. Applications

22. Solution-Based Synthesis of Nano-Sized TiO₂ Anatase in Fluorinating Media

• 1. Introduction
• 2. General Interests of Fluorinating Media
• 3. Evidences for the Stabilization of Fluoride in Anatase Featuring Cationic Vacancies
• 4. Conclusion

23. Ionic Liquid Materials Based on Fluoroanions

• 1. Introduction
• 2. Syntheses and Structures of Ionic Liquids Based on Fluorohydrogenate Anions
• 3. Properties of Ionic Liquids Based on Fluorohydrogenate Anions
• 4. Syntheses of Ionic Liquids Based on Fluorocomplex and Oxofluorocomplex Anions
• 5. Structures and Properties of Ionic Liquids Based on Fluorocomplex Anions
• 6. Conclusions

24. Reactivity of Surface Fluorinated TiO₂ and TiAl Particles

• 1. Surface Fluorination of TiO₂ Particles
• 2. Surface Fluorination of TiAl Alloy Particles
• 3. Conclusions

25. Chemical and Electrochemical Stability of Copper in Molten KF-2HF

• 1. Introduction
• 2. Experimental Section
• 3. Results
• 4. Conclusions