8 4 Introduction of Trifluoromethylthio Group into Organic Molecules 4.1 Introduction 4.2 Nucleophilic Trifluoromethylthiolation 4.2.1 Preparation of Nucleophilic Trifluoromethylthiolating Reagent 4.2.1.1 Preparation of Hg(SCF3)2, AgSCF3, and CuSCF3 4.2.1.2 Preparation of MSCF3 (M = K, Cs, Me4N, and S(NMe2)3) 4.2.1.3 Preparation of Stable Trifluoromethylthiolated Copper(I) Complexes 4.2.2 Formation of C(sp2)‐SCF3 by Nucleophilic Trifluoromethylthiolating Reagents 4.2.2.1 Reaction of CuSCF3 with Aryl Halides 4.2.2.2 Sandmeyer‐Type Trifluoromethylthiolation 4.2.2.3 Transition Metal‐Catalyzed Trifluoromethylthiolation 4.2.2.4 Oxidative Trifluoromethylthiolation 4.2.2.5 Transition Metal‐Catalyzed Trifluoromethylthiolation of Arenes via C–H Activation 4.2.2.6 Miscellaneous Methods for the Formation or Aryl Trifluoromethylthioethers via Nucleophilic Trifluoromethylthiolating Reagents 4.2.3 Formation of C(sp3)‐SCF3 by Nucleophilic Trifluoromethylthiolating Reagents 4.2.3.1 Reaction of CuSCF3 with Activated Alkylated Halides 4.2.3.2 Reaction of MSCF3 with Unactivated Alkyl Halides 4.2.3.3 Nucleophilic Dehydroxytrifluoromethylthiolation of Alcohols 4.2.3.4 Nucleophilic Trifluoromethylthiolation of Alcohol Derivatives 4.2.3.5 Nucleophilic Trifluoromethylthiolation of α‐Diazoesters 4.2.3.6 Formation or Alkyl Trifluoromethylthioethers via In Situ Generated Nucleophilic Trifluoromethylthiolating Reagent 4.2.3.7 Formation of Alkyl Trifluoromethylthioethers via C–H Bond Trifluoromethylthiolation 4.3 Electrophilic Trifluoromethylthiolating Reagents 4.3.1 CF3SCl 4.3.2 CF3SSCF3 4.3.3 Haas Reagent 4.3.4 Munavalli Reagent 4.3.5 Billard Reagent 4.3.6 Shen Reagent 4.3.7 Shen Reagent‐II 4.3.8 Optically Active Pure Trifluoromethylthiolation Reagents 4.3.9 Lu–Shen Reagent 4.3.10 α‐Cumyl Bromodifluoromethanesulfenate 4.3.11 Shibata Reagent 4.3.12 In Situ‐Generated Electrophilic Trifluoromethylthiolating Reagents 4.3.12.1 AgSCF3 + TCCA 4.3.12.2 Application of AgSCF3 + NCS 4.3.12.3 Application of Langlois Reagent (CF3SO2Na) with Phosphorus Reductants 4.3.12.4 Use of CF3SO2Cl with Phosphorus Reductants 4.3.12.5 Reagent Based on CF3SOCl and Phosphorus Reductants 4.4 Radical Trifluoromethylthiolation 4.4.1 Trifluoromethylthiolation by AgSCF3/S2O82−‐ 4.4.2 Electrophilic Reagents Involved in Radical Trifluoromethylthiolation 4.4.3 Visible Light‐Promoted Trifluoromethylthiolation by Using Electrophilic Reagents 4.5 Summary and Prospect References
9 5 Bifunctionalization‐Based Catalytic Fluorination and Trifluoromethylation 5.1 Introduction 5.2 Palladium‐Catalyzed Fluorination, Trifluoromethylation, and Trifluoromethoxylation of Alkenes 5.2.1 Palladium‐Catalyzed Fluorination of Alkenes 5.2.2 Palladium‐Catalyzed Trifluoromethylation of Alkenes 5.2.3 Palladium‐Catalyzed Trifluoromethoxylation of Alkenes 5.3 Copper‐Catalyzed Trifluoromethylative Functionalization of Alkenes