Organofluorine Chemistry

Kálmán J. Szabó is professor at the Department of Organic Chemistry at the Arrhenius Laboratory, Stockholm University (Sweden), since 2003. His major research interests are method development in organic synthesis, catalytic reactions, organoboron and organofluorine (including fluorine-18) chemistry. He is a member of the Royal Swedish Academy of Sciences and has authored over 150 publications. He is the editor of the book Pincer and Pincer-Type Complexes (Wiley-VCH).Nicklas Selander is an assistant professor at the Department of Organic Chemistry at Stockholm University (Sweden), since 2018. His research interests include organic synthesis methodology, catalysis, and radical chemistry.

• Preface xiii1 The Development of New Reagents and Reactions for Synthetic Organofluorine Chemistry by Understanding the Unique Fluorine Effects 1Qiqiang Xie and Jinbo Hu1.1 Introduction 11.2 The Unique Fluorine Effects in Organic Reactions 31.3 The Relationships Among Fluoroalkylation, Fluoroolefination, and Fluorination 91.4 Conclusions 20References 202 Perfluoroalkylation Using Perfluorocarboxylic Acids and Anhydrides 23Shintaro Kawamura and Mikiko Sodeoka2.1 Introduction 232.2 Perfluoroalkylation with Perfluorocarboxylic Acids 232.3 Perfluoroalkylation with Perfluorocarboxylic Anhydride 392.4 Summary and Prospects 43References 433 Chemistry of OCF3, SCF3, and SeCF3 Functional Groups 49Fabien Toulgoat, François Liger and Thierry Billard3.1 Introduction 493.2 CF3O Chemistry 493.3 CF3S Chemistry 633.4 CF3Se Chemistry 693.5 Summary and Conclusions 85References 864 Introduction of Trifluoromethylthio Group into Organic Molecules 99Hangming Ge, He Liu and Qilong Shen4.1 Introduction 994.2 Nucleophilic Trifluoromethylthiolation 994.3 Electrophilic Trifluoromethylthiolating Reagents 1204.4 Radical Trifluoromethylthiolation 1514.5 Summary and Prospect 165References 1655 Bifunctionalization-Based Catalytic Fluorination and Trifluoromethylation 173Pinhong Chen and Guosheng Liu5.1 Introduction 1735.2 Palladium-Catalyzed Fluorination, Trifluoromethylation, and Trifluoromethoxylation of Alkenes 1735.3 Copper-Catalyzed Trifluoromethylative Functionalization of Alkenes 1835.4 Summary and Conclusions 197References 1976 Fluorination, Trifluoromethylation, and Trifluoromethylthiolation of Alkenes, Cyclopropanes, and Diazo Compounds 201Kálmán J. Szabó6.1 Introduction 2016.2 Fluorination of Alkenes, Cyclopropanes, and Diazocarbonyl Compounds 2026.3 Fluorination-Based Bifunctionalization of Diazocarbonyl Compounds 2096.4 Trifluoromethylation of Alkenes, Alkynes, and Diazocarbonyl Compounds with the Togni Reagent 2126.5 Bifunctionalization-Based Trifluoromethylthiolation of Diazocarbonyl Compounds 2186.6 Summary 220References 2217 Photoredox Catalysis in Fluorination and Trifluoromethylation Reactions 225Takashi Koike and Munetaka Akita7.1 Introduction 2257.2 Fluorination 2267.3 Trifluoromethylation 2347.4 Summary and Outlook 239References 2398 Asymmetric Fluorination Reactions 241Edward Miller and F. Dean Toste8.1 Introduction 2418.2 Electrophilic Fluorination 2428.3 Nucleophilic Fluorination 2698.4 Summary and Conclusions 274References 2769 The Self-Disproportionation of Enantiomers (SDE): Fluorine as an SDE-Phoric Substituent 281Jianlin Han, Santos Fustero, Hiroki Moriwaki, Alicja Wzorek, Vadim A. Soloshonok and Karel D. Klika9.1 Introduction 2819.2 General Concepts and the Role of Fluorine in the Manifestation of the SDE 2839.3 The SDE Phenomenon 2859.4 The SIDA Phenomenon 2949.5 Conclusions and Recommendations 296References 29910 DFT Modeling of Catalytic Fluorination Reactions: Mechanisms, Reactivities, and Selectivities 307Yueqian Sang, Biying Zhou, Meng-Meng Zheng, Xiao-Song Xue and Jin-Pei Cheng10.1 Introduction 30710.2 DFT Modeling of Transition Metal-Catalyzed Fluorination Reactions 30810.3 DFT Modeling of Organocatalytic Fluorination Reactions 34010.4 DFT Modeling of Enzymatic Fluorination Reaction 35410.5 Conclusions 357Acknowledgments 357References 35811 Current Trends in the Design of Fluorine-Containing Agrochemicals 363Peter Jeschke11.1 Introduction 36311.2 Role of Fluorine in the Design of Modern Agrochemicals 36311.3 Fluorinated Modern Agrochemicals 36511.4 Summary and Prospects 389References 39012 Precision Radiochemistry for Fluorine-18 Labeling of PET Tracers 397Jian Rong, Ahmed Haider and Steven Liang12.1 Introduction 39712.2 Electrophilic 18F-Fluorination with [18F]F2 and [18F]F2-Derived Reagents 39812.3 Nucleophilic Aliphatic 18F-Fluorination 39912.4 Nucleophilic Aromatic 18F-Fluorination with [18F]Fluoride 40512.5 18F-Labeling of Multifluoromethyl Motifs with [18F]Fluoride 41812.6 Summary and Conclusions 421References 421Index 427