Table of Contents
1 Cover
4 Preface
5 1 The Development of New Reagents and Reactions for Synthetic Organofluorine Chemistry by Understanding the Unique Fluorine Effects 1.1 Introduction 1.2 The Unique Fluorine Effects in Organic Reactions 1.2.1 Fluorine‐Enabled Stability of “CuCF3” in Water, and the Unusual Water‐Promoted Trifluoromethylation 1.2.2 Fluorine Enables β‐Fluoride Elimination of Organocopper Species 1.2.3 The “Negative Fluorine Effect” Facilitates the α‐Elimination of Fluorocarbanions to Generate Difluorocarbene Species 1.2.4 Tackling the β‐Fluoride Elimination of Trifluoromethoxide Anion via a Fluoride Ion‐Mediated Process 1.3 The Relationships Among Fluoroalkylation, Fluoroolefination, and Fluorination 1.3.1 From Fluoroalkylation to Fluoroolefination 1.3.2 From Fluoroolefination to Fluoroalkylation 1.3.3 From Fluoroalkylation to Fluorination 1.4 Conclusions References
6 2 Perfluoroalkylation Using Perfluorocarboxylic Acids and Anhydrides 2.1 Introduction 2.2 Perfluoroalkylation with Perfluorocarboxylic Acids 2.2.1 Electrochemical Reactions 2.2.1.1 Reactions of Alkenes and Alkynes 2.2.1.2 Reaction of Aromatic Compounds 2.2.2 Reactions Using XeF2 2.2.3 Reactions Using Copper and Silver Salts 2.2.3.1 Using Copper Salts 2.2.3.2 Using Silver Salts 2.2.4 Photochemical Reactions 2.2.5 Other Methods 2.2.5.1 Hydro‐Trifluoromethylation of Fullerene 2.2.5.2 Metal‐Free Aryldifluoromethylation Using S2O82− 2.3 Perfluoroalkylation with Perfluorocarboxylic Anhydride 2.3.1 Reactions Using Perfluorocarboxylic Anhydride/Urea·H2O2 2.3.2 Photocatalytic Reactions Using Perfluorocarboxylic Anhydride/Pyridine N‐oxide 2.4 Summary and Prospects References
7 3 Chemistry of OCF3, SCF3, and SeCF3 Functional Groups 3.1 Introduction 3.2 CF3O Chemistry 3.2.1 De Novo Construction 3.2.1.1 Trifluorination of Alcohol Derivatives 3.2.1.2 Fluorination of Difluorinated Compounds 3.2.2 Indirect Methods 3.2.2.1 O‐(Trifluoromethyl)dibenzofuranium Salts 3.2.2.2 Hypervalent Iodine Trifluoromethylation Reagents 3.2.2.3 CF3SiMe3 3.2.3 Direct Trifluoromethoxylation 3.2.3.1 Difluorophosgene and Derivatives 3.2.3.2 Trifluoromethyl Hypofluorite and Derivatives 3.2.3.3 Trifluoromethyl Triflate (TFMT) 3.2.3.4 Trifluoromethoxide Salts Derived from TFMT or Difluorophosgene 3.2.3.5 Trifluoromethyl Arylsulfonates (TFMSs) 3.2.3.6 Trifluoromethylbenzoate (TFBz) 3.2.3.7 2,4‐Dinitro(trifluoromethoxy)benzene (DNTFB) 3.2.3.8 (Triphenylphosphonio)difluoroacetate (PDFA) 3.2.3.9 N‐Trifluoromethoxylated Reagents 3.3 CF3S Chemistry 3.3.1 Indirect Methods 3.3.2 Direct Trifluoromethylthiolation 3.3.2.1 CF3SAg, CF3SCu, CF3SNR4 3.3.2.2 Trifluoromethanesulfenamides 3.3.2.3 N‐Trifluoromethylthiophthalimide 3.3.2.4 N‐Trifluoromethylthiosaccharin 3.3.2.5 N‐Trifluoromethylthiobis(phenylsulfonyl)amide 3.4 CF3Se Chemistry 3.4.1 Introduction 3.4.2 Indirect Synthesis of CF3Se Moiety 3.4.2.1 Ruppert–Prakash Reagent (CF3SiMe3)