10 6 Fluorination, Trifluoromethylation, and Trifluoromethylthiolation of Alkenes, Cyclopropanes, and Diazo Compounds 6.1 Introduction 6.2 Fluorination of Alkenes, Cyclopropanes, and Diazocarbonyl Compounds 6.2.1 Application of Fluoro‐Benziodoxole for Fluorination of Alkenes 6.2.1.1 Geminal Difluorination of Styrene Derivatives 6.2.1.2 Iodofluorination of Alkenes 6.2.1.3 Fluorocyclization with C–N, C–O, and C–C Bond Formation 6.2.2 Fluorinative Cyclopropane Opening 6.2.3 Fluorine‐18 Labeling with Fluorobenziodoxole 6.3 Fluorination‐Based Bifunctionalization of Diazocarbonyl Compounds 6.3.1 Rhodium‐Catalyzed Geminal Oxyfluorination Reactions 6.3.2 [18F]Fluorobenziodoxole for Synthesis of α‐Fluoro Ethers 6.4 Trifluoromethylation of Alkenes, Alkynes, and Diazocarbonyl Compounds with the Togni Reagent 6.4.1 Bifunctionalization of C–C Multiple Bonds 6.4.1.1 Oxytrifluoromethylation of Alkenes and Alkynes 6.4.1.2 Cyanotrifluoromethylation of Styrenes 6.4.1.3 C–H Trifluoromethylation of Benzoquinone Derivatives 6.4.2 Geminal Oxytrifluoromethylation of Diazocarbonyl Compounds 6.5 Bifunctionalization‐Based Trifluoromethylthiolation of Diazocarbonyl Compounds 6.5.1 Multicomponent Approach for Geminal Oxy‐Trifluormethylthiolation 6.5.2 Simultaneous Formation of C–C and C–SCF3 Bonds via Hooz‐Type Reaction 6.6 Summary References
11 7 Photoredox Catalysis in Fluorination and Trifluoromethylation Reactions 7.1 Introduction 7.2 Fluorination 7.2.1 Fluorination Through Direct HAT Process by Excited Photocatalyst 7.2.2 Fluorination Through Photoredox Processes 7.3 Trifluoromethylation 7.3.1 Trifluoromethylation of Aromatic Compounds 7.3.2 Trifluoromethylative Substitution of Alkyl Bromides 7.4 Summary and Outlook References
12 8 Asymmetric Fluorination Reactions 8.1 Introduction 8.2 Electrophilic Fluorination 8.2.1 Stoichiometric Asymmetric Fluorination 8.2.1.1 Chiral Auxiliary 8.2.1.2 Chiral Reagents 8.2.2 Catalytic Electrophilic Fluorination 8.2.2.1 Organocatalytic Fluorination 8.2.2.2 Transition Metal‐Catalyzed Fluorinations 8.3 Nucleophilic Fluorination 8.3.1 Metal‐Catalyzed Nucleophilic Fluorination 8.3.1.1 Ring Opening of Strained Ring Systems 8.3.1.2 Allylic Functionalization 8.3.2 Organocatalytic Nucleophilic Fluorination 8.4 Summary and Conclusions References
13 9 The Self‐Disproportionation of Enantiomers (SDE): Fluorine as an SDE‐Phoric Substituent 9.1 Introduction 9.2 General Concepts and the Role of Fluorine in the Manifestation of the SDE 9.3 The SDE Phenomenon 9.3.1 SDE via Distillation 9.3.2 SDE via Sublimation 9.3.3 SDE via Chromatography 9.3.3.1 SDEvC for Compounds Containing a –CF3 Moiety 9.3.3.2 SDEvC for Compounds Containing a Cq–F1/2 Moiety 9.3.3.3 SDEvC for Compounds Containing a –COCF3 Moiety 9.4 The SIDA Phenomenon 9.5 Conclusions and Recommendations References
14 10 DFT Modeling of Catalytic Fluorination Reactions: Mechanisms, Reactivities, and Selectivities