Modern Fluoroorganic Chemistry

402 Pages·2013·3.899 MB·English

by  Peer Kirsch

PeerKirsch
ModernFluoroorganicChemistry
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Peer Kirsch
Modern Fluoroorganic Chemistry
Synthesis, Reactivity, Applications
Second, Completely Revised and Enlarged Edition
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v
ToAnnetteandAlexander
‘‘Thefuryofthechemicalworldistheelementfluorine.Itexistspeacefullyinthecompany
with calcium in fluorspar and alsoin a few other compounds;but when isolated,as it
recentlyhasbeen,itisarabidgasthatnothingcanresist.’’
ScientificAmerican,April1888.
‘‘Fluorineleavesnobodyindifferent;itinflamesemotionsbethataffectionsoraversions.
As a substituent, it is rarely boring, always good for a surprise, but often completely
unpredictable.’’
M.Schlosser,Angew.Chem.Int.Ed.1998,37,1496–1513.

VII
Contents
PrefacetotheSecondEdition XIII
PrefacetotheFirstEdition XV
Abbreviations XVII
1 Introduction 1
1.1 WhyOrganofluorineChemistry? 1
1.2 History 1
1.3 TheBasicMaterials 3
1.3.1 HydrofluoricAcid 3
1.3.2 Fluorine 5
1.4 TheUniquePropertiesofOrganofluorineCompounds 7
1.4.1 PhysicalProperties 7
1.4.2 ChemicalProperties 13
1.4.3 EcologicalImpact 15
1.4.3.1 OzoneDepletionbyChlorofluorocarbons 15
1.4.3.2 GreenhouseEffect 17
1.4.4 PhysiologicalProperties 18
1.4.5 AnalysisofFluorochemicals:19FNMRSpectroscopy 20
References 21
PartI SynthesisofComplexOrganofluorineCompounds 25
2 IntroductionofFluorine 27
2.1 PerfluorinationandSelectiveDirectFluorination 27
2.2 ElectrochemicalFluorination(ECF) 34
2.3 NucleophilicFluorination 36
2.3.1 FinkelsteinExchange 36
2.3.2 ‘‘Naked’’Fluoride 36
2.3.3 LewisAcid-AssistedFluorination 39
2.3.4 The‘‘GeneralFluorineEffect’’ 41
2.3.5 Amine–HydrogenFluorideandEther–HydrogenFluoride
Reagents 42
VIII Contents
2.3.6 Hydrofluorination,Halofluorination,andEpoxideRingOpening 43
2.4 SynthesisandReactivityofFluoroaromaticCompounds 46
2.4.1 SynthesisofFluoroaromaticCompounds 46
2.4.2 ReductiveAromatization 47
2.4.3 TheBalz–SchiemannReaction 47
2.4.4 TheFluoroformateProcess 49
2.4.5 TransitionMetal-CatalyzedAromaticFluorination 49
2.4.6 TheHalexProcess 55
2.4.7 ThinkNegative! – ‘‘Orthogonal’’ReactivityofPerfluoroaromaticand
PerfluoroolefinicSystems 55
2.4.8 The‘‘SpecialFluorineEffect’’ 58
2.4.9 AromaticNucleophilicSubstitution 59
2.4.10 ActivationoftheCarbon–FluorineBondbyTransitionMetals 63
2.4.10.1 ElectrophilicallyActivatedArylationbyFluoroarenes 63
2.4.11 ActivationofFluoroaromaticCompoundsbyOrtho-Metalation 64
2.5 TransformationsofFunctionalGroups 67
2.5.1 HydroxyintoFluoro 67
2.5.1.1 Two-StepActivation–Fluorination 68
2.5.1.2 α,α-Difluoroalkylamineandα-FluoroenamineReagents 68
2.5.1.3 SulfurTetrafluoride,DAST,andRelatedReagents 71
2.5.1.4 Amine–HydrogenFluorideReagents 73
2.5.2 ConversionofCarbonylintogem-Difluoromethylene 74
2.5.2.1 SulfurTetrafluoride,DAST,andRelatedReagents 74
2.5.3 CarboxylintoTrifluoromethyl 77
2.5.4 OxidativeFluorodesulfuration 78
2.6 ‘‘Electrophilic’’Fluorination 85
2.6.1 XenonDifluoride 85
2.6.2 PerchlorylFluorideandHypofluorides 86
2.6.3 ‘‘NF’’-Reagents 88
References 98
3 Perfluoroalkylation 107
3.1 RadicalPerfluoroalkylation 107
3.1.1 Structure,Properties,andReactivityofPerfluoroalkylRadicals 107
3.1.2 PreparativelyUsefulReactionsofPerfluoroalkylRadicals 110
3.1.3 ‘‘Inverse’’RadicalAdditionofAlkylRadicalstoPerfluoroolefins 115
3.2 NucleophilicPerfluoroalkylation 118
3.2.1 Properties,Stability,andReactivityofFluorinatedCarbanions 118
3.2.2 PerfluoroalkylMetalCompounds 120
3.2.3 Perfluoroalkylsilanes 130
3.3 ‘‘Electrophilic’’Perfluoroalkylation 139
3.3.1 PropertiesandStabilityofFluorinatedCarbocations 139
3.3.2 ArylperfluoroalkyliodoniumSalts 142
3.3.3 PerfluoroalkylSulfonium,Selenonium,Telluronium,andOxonium
Salts 149