Читать книгу Organofluorine Chemistry - Группа авторов - Страница 2

1  Cover

2  Title Page

3  Copyright

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) 3.4.2.2 Fluoroform (HCF3) 3.4.2.3 Other Reagents Involved in CF3− Anion Generation 3.4.2.4 Sodium Trifluoromethylsulfinate (CF3SO2Na) 3.4.3 Direct Introduction of the CF3Se Moiety 3.4.3.1 Trifluoromethyl Selenocopper DMF Complex 3.4.3.2 Trifluoromethyl Selenocopper Bipyridine Complex: [bpyCuSeCF3]2 3.4.3.3 Tetramethylammonium Trifluoromethylselenolate [(NMe4)(SeCF3)] 3.4.3.4 In Situ Generation of CF3Se− Anion from Elemental Selenium 3.4.3.5 Trifluoromethylselenyl Chloride (CF3SeCl) 3.4.3.6 Benzyltrifluoromethylselenide (CF3SeBn) 3.4.3.7 Trifluoromethylselenotoluenesulfonate (CF3SeTs) 3.4.3.8 Benzylthiazolium Salt BT‐SeCF3 3.5 Summary and Conclusions References

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 5.3.1 Copper‐Catalyzed Trifluoromethylamination of Alkenes 5.3.2 Copper‐Catalyzed Trifluoromethyloxygenation of Alkenes 5.3.3 Copper‐Catalyzed Trifluoromethylcarbonation of Alkenes 5.3.4 Enantioselective Copper‐Catalyzed Trifluoromethylation of Alkenes 5.4 Summary and Conclusions References

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 10.1 Introduction 10.2 DFT Modeling of Transition Metal‐Catalyzed Fluorination Reactions 10.2.1 Ti‐Catalyzed Fluorination Reaction 10.2.2 Mn‐Catalyzed Fluorination Reactions 10.2.3 Fe‐Catalyzed Fluorination Reactions 10.2.4 Rh‐Catalyzed Fluorination Reactions 10.2.5 Ir‐Catalyzed Fluorination Reactions 10.2.6 Pd‐Catalyzed Fluorination Reactions 10.2.6.1 Pd‐Catalyzed Nucleophilic Fluorination 10.2.6.2 Pd‐Catalyzed Electrophilic Fluorination 10.2.7 Cu‐Catalyzed Fluorination Reactions 10.2.7.1 Cu‐Catalyzed Nucleophilic Fluorination 10.2.7.2 Cu‐Mediated Radical Fluorination 10.2.8 Ag‐Catalyzed Fluorination Reactions 10.2.9 Zn‐Catalyzed Fluorination Reactions 10.3 DFT Modeling of Organocatalytic Fluorination Reactions 10.3.1 Fluorination Reactions Catalyzed by Chiral Amines 10.3.1.1 Chiral Secondary Amines‐Catalyzed Fluorination Reactions 10.3.1.2 Chiral Primary Amines‐Catalyzed Fluorination Reactions 10.3.2 Tridentate Bis‐Urea Catalyzed Fluorination Reactions 10.3.3 Hypervalent Iodine‐Catalyzed Fluorination Reactions 10.3.4 N‐Heterocyclic Carbene‐Catalyzed Fluorination Reactions 10.4 DFT Modeling of Enzymatic Fluorination Reaction 10.5 Conclusions Acknowledgments References

15  11 Current Trends in the Design of Fluorine‐Containing Agrochemicals 11.1 Introduction 11.2 Role of Fluorine in the Design of Modern Agrochemicals 11.3 Fluorinated Modern Agrochemicals 11.3.1 Herbicides Containing Fluorine 11.3.1.1 Acetohydroxyacid Synthase/Acetolactate Synthase Inhibitors 11.3.1.2 Protoporphyrinogen Oxidase Inhibitors 11.3.1.3 Cellulose Biosynthesis Inhibitors 11.3.1.4 Very Long‐Chain Fatty Acid Synthesis Inhibitors 11.3.1.5 Auxin Herbicides 11.3.1.6 Hydroxyphenylpyruvate Dioxygenase Inhibitors 11.3.1.7 Selected Fluorine‐Containing Herbicide Development Candidates 11.3.2 Fungicides Containing Fluorine 11.3.2.1 Fungicidal Succinate Dehydrogenase Inhibitors 11.3.2.2 Complex III Inhibitors 11.3.2.3 Sterolbiosynthesis (Sterol‐C14‐Demethylase) Inhibitors 11.3.2.4 Polyketide Synthase Inhibitors 11.3.2.5 Oxysterol‐Binding Protein Inhibitors 11.3.2.6 Selected Fluorine‐Containing Fungicide Development Candidates 11.3.3 Insecticides Containing Fluorine 11.3.3.1 Nicotinic Acetylcholine Receptor Competitive Modulators 11.3.3.2 Ryanodine Receptor (RyR) Modulators 11.3.3.3 GABA‐Gated CI‐Channel Allosteric Modulators 11.3.3.4 Selected Fluorine‐Containing Insecticide Development Candidates 11.3.4 Acaricides Containing Fluorine 11.3.4.1 Mitochondrial Complex II Electron Transport Inhibitors 11.3.4.2 Selected Fluorine‐Containing Acaricide Development Candidates 11.3.5 Nematicides Containing Fluorine 11.3.5.1 Nematicides with Unknown Biochemical MoA 11.3.5.2 Nematicidal Succinate Dehydrogenase Inhibitors 11.3.5.3 Selected Fluorine‐Containing Nematicide Development Candidates 11.4 Summary and Prospects References

16  12 Precision Radiochemistry for Fluorine‐18 Labeling of PET Tracers 12.1 Introduction 12.2 Electrophilic 18F‐Fluorination with [18F]F2 and [18F]F2‐Derived Reagents 12.3 Nucleophilic Aliphatic 18F‐Fluorination 12.3.1 Transition Metal‐Free Nucleophilic Aliphatic Substitution with [18F]Fluoride 12.3.2 Transition Metal‐Mediated Aliphatic 18F‐Fluorination 12.4 Nucleophilic Aromatic 18F‐Fluorination with [18F]Fluoride 12.4.1 Transition Metal‐Free Nucleophilic Aromatic 18F‐Fluorination with [18F]Fluoride 12.4.2 Transition Metal‐Mediated Aromatic 18F‐Fluorination 12.5 18F‐Labeling of Multifluoromethyl Motifs with [18F]Fluoride 12.6 Summary and Conclusions References

17  Index

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