Modern Oxidation Methods, 2nd Edition

483 Pages·2010·5.61 MB·English

by  Jan-Erling Backvall

B Edited by Jan-Erling Bäckvall
ä
W c
hile rust is an unwanted oxidation reaction, there are also many other k
useful oxidation reactions that are extremely important and number v
a
among the most commonly used reactions in the chemical industry.
l
l Modern
This completely revised, updated second edition now includes addi-
(
tional sections on industrial oxidation and biochemical oxidation. E
Edited by one of the world leaders in the field, high-quality contri- d
.
butions cover every important aspect from classical to green chemistry )
methods:
Oxidation Methods
● Recent Developments in Metal-catalyzed Dihydroxylation of Alkenes
● Transition Metal-Catalyzed Epoxidation of Alkenes
● Organocatalytic Oxidation. Ketone-Catalyzed Asymmetric Epoxida-
tion of Alkenes and Synthetic Applications
● Catalytic Oxidations with Hydrogen Peroxide in Fluorinated Alcohol
Solvents
● Modern Oxidation of Alcohols using Environmentally Benign
Oxidants Second Edition
● Aerobic Oxidations and Related Reactions Catalyzed by N-Hydro-
xyphthalimide
● Ruthenium-Catalyzed Oxidation for Organic Synthesis
● Selective Oxidation of Amines and Sulfi des
● Liquid Phase Oxidation Reactions Catalyzed by Polyoxometalates
M
● Oxidation of Carbonyl Compounds
● Manganese-Catalyzed Oxidation with Hydrogen Peroxide o
d
● Biooxidation with Cytochrome P450 Monooxygenases
e
r
By providing an overview of this vast topic, the book represents an n
unparalleled aid for organic, catalytic and biochemists working in the
O
field.
x
i
d
a
Jan-Erling Bäckvall is Professor of Organic Chemistry at Stockholm University, where he is Head
t
of the Research. He is renowned for his contribution to organopalladium chemistry and catalytic i
oxidation reactions where he has done mechanistic work and developed new reactions. More o
recently efficient systems for dynamic kinetic resolution of alcohols based on combined ruthenium n
and enzyme catalysis were developed in his laboratory. Jan-Erling Bäckvall has published about
M
380 papers. For his contribution to research he was elected a Member of The Royal Swedish
Academy of Sciences, a Member of the Nobel Committee for Chemistry, a Fellow of the Royal e
Society of Sciences, Sweden, a Member of “Fysiografiska sällskapet”, Sweden and a Foreign Mem- t
ber of the Finnish Academy of Science and Letters and received many prizes, awards and honors. h
o
d
s
ISBN 978-3-527-32320-3
www.wiley-vch.de

Edited by
Jan-Erling Ba¨ckvall
Modern Oxidation Methods
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Edited by
Jan-Erling Bäckvall
Modern Oxidation Methods
2nd completely revised and enlarged edition
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V
Contents
Preface XI
List of Contributors XIII
1 RecentDevelopmentsinMetal-catalyzedDihydroxylationofAlkenes 1
ManKinTse,KristinSchröder,andMatthiasBeller
1.1 Introduction 1
1.2 EnvironmentallyFriendlyTerminalOxidants 3
1.2.1 HydrogenPeroxide 3
1.2.2 Hypochlorite 5
1.2.3 Chlorite 8
1.2.4 OxygenorAir 9
1.3 SupportedOsmiumCatalyst 16
1.3.1 Nitrogen-groupDonatingSupport 16
1.3.2 MicroencapsulatedOsO 17
4
1.3.3 SupportsBearingAlkenes 19
1.3.4 ImmobilizationbyIonicInteraction 21
1.4 IonicLiquid 22
1.5 RutheniumCatalysts 23
1.6 IronCatalysts 26
1.7 Conclusions 32
References 32
2 TransitionMetal-CatalyzedEpoxidationofAlkenes 37
HansAdolfsson
2.1 Introduction 37
2.2 ChoiceofOxidantforSelectiveEpoxidation 38
2.3 EpoxidationsofAlkenesCatalyzedbyEarlyTransitionMetals 39
2.4 MolybdenumandTungsten-CatalyzedEpoxidations 42
2.4.1 HomogeneousCatalysts–HydrogenPeroxideastheTerminal
Oxidant 42
2.4.2 HeterogeneousCatalysts 46
2.5 Manganese-CatalyzedEpoxidations 47
VI Contents
2.6 Rhenium-CatalyzedEpoxidations 52
2.6.1 MTOasEpoxidationCatalyst–OriginalFindings 54
2.6.2 TheInfluenceofHeterocyclicAdditives 55
2.6.3 TheRoleoftheAdditive 58
2.6.4 OtherOxidants 59
2.6.5 Solvents/Media 61
2.6.6 SolidSupport 63
2.6.7 AsymmetricEpoxidationsUsingMTO 64
2.7 Iron-CatalyzedEpoxidations 64
2.7.1 Iron-CatalyzedAsymmetricEpoxidations 72
2.8 Ruthenium-CatalyzedEpoxidations 74
2.9 EpoxidationsUsingLateTransitionMetals 76
2.10 ConcludingRemarks 79
References 80
3 OrganocatalyticOxidation.Ketone-CatalyzedAsymmetricEpoxidation
ofAlkenesandSyntheticApplications 85
YianShi
3.1 Introduction 85
3.2 CatalystDevelopment 86
3.3 SyntheticApplications 98
3.4 Conclusion 109
References 109
4 CatalyticOxidationswithHydrogenPeroxideinFluorinated
AlcoholSolvents 117
AlbrechtBerkessel
4.1 Introduction 117
4.2 PropertiesofFluorinatedAlcohols 118
4.2.1 ADetailedLookattheHydrogenBondDonorFeaturesofHFIP 120
4.3 EpoxidationofAlkenesinFluorinatedAlcoholSolvents 123
4.3.1 AlkeneEpoxidationwithHydrogenPeroxide–intheAbsence
ofFurtherCatalysts 123
4.3.1.1 OntheMechanismofEpoxidationCatalysisbyFluorinated
Alcohols 123
4.3.2 AlkeneEpoxidationwithHydrogenPeroxide–inthePresence
ofFurtherCatalysts 129
4.3.2.1 ArsinesandArsineOxidesasCatalysts 129
4.3.2.2 ArsonicAcidsasCatalysts 130
4.3.2.3 Diselenides/SeleninicAcidsasCatalysts 132
4.3.2.4 RheniumCompoundsasCatalysts 133
4.3.2.5 FluoroketonesasCatalysts 135
4.4 SulfoxidationofThioethersinFluorinatedAlcoholSolvents 136
4.5 Baeyer-VilligerOxidationofKetonesinFluorinated
AlcoholSolvents 136
Contents VII
4.5.1 Acid-CatalyzedBaeyer-VilligerOxidationofKetonesinFluorinated
AlcoholSolvents–Mechanism 139
4.5.2 Baeyer-VilligerOxidationofKetonesinFluorinatedAlcohol
Solvents–CatalysisbyArsonicandSeleninicAcids 141
4.6 Epilog 142
References 143
5 ModernOxidationofAlcoholsusingEnvironmentally
BenignOxidants 147
IsabelW.C.E.ArendsandRogerA.Sheldon
5.1 Introduction 147
5.2 OxoammoniumbasedOxidationofAlcohols–TEMPOasCatalyst 147
5.3 Metal-MediatedOxidationofAlcohols–Mechanism 151
5.4 Ruthenium-CatalyzedOxidationswithO2 153
5.5 Palladium-CatalyzedOxidationswithO2 163
5.5.1 GoldNanoparticlesasCatalysts 169
5.6 Copper-CatalyzedOxidationswithO2 170
5.7 OtherMetalsasCatalystsforOxidationwithO2 174
5.8 CatalyticOxidationofAlcoholswithHydrogenPeroxide 176
5.8.1 BiocatalyticOxidationofAlcohols 179
5.9 ConcludingRemarks 180
References 180
6 AerobicOxidationsandRelatedReactionsCatalyzedby
N-Hydroxyphthalimide 187
YasutakaIshii,SatoshiSakaguchi,andYasushiObora
6.1 Introduction 187
6.2 NHPI-CatalyzedAerobicOxidation 188
6.2.1 AlkaneOxidationswithDioxygen 188
6.2.2 OxidationofAlkylarenes 193
6.2.2.1 SynthesisofTerephthalicAcid 196
6.2.2.2 OxidationofMethylpyridinesandMethylquinolines 199
6.2.2.3 OxidationofHydroaromaticandBenzylicCompounds 201
6.2.3 PreparationofAcetylenicKetonesbyDirectOxidationofAlkynes 203
6.2.4 OxidationofAlcohols 205
6.2.5 EpoxidationofAlkenesusingDioxygenasTerminalOxidant 208
6.2.6 Baeyer-VilligerOxidationofKAOil 209
6.2.7 Preparationofe-CaprolactamPrecursorfromKAOil 210
6.3 FunctionalizationofAlkanesCatalyzedbyNHPI 211
6.3.1 CarboxylationofAlkaneswithCOandO 211
2
6.3.2 FirstCatalyticNitrationofAlkanesusingNO 212
2
6.3.3 SulfoxidationofAlkanesCatalyzedbyVanadium 214
6.3.4 ReactionofNOwithOrganicCompounds 217
6.3.5 NitrosationofCycloalkaneswitht-BuONO 219
6.3.6 Ritter-typeReactionwithCeriumAmmoniumNitrate(CAN) 220
VIII Contents
6.4 Carbon-CarbonBond-FormingReactionviaCatalyticCarbon
RadicalsGenerationAssistedbyNHPI 222
6.4.1 OxyalkylationofAlkeneswithAlkanesandDioxygen 222
6.4.2 Synthesisofa-Hydroxy-c-lactonesbyAdditionofa-Hydroxy
CarbonRadicalstoUnsaturatedEsters 223
6.4.3 HydroxyacylationofAlkenesusing1,3-DioxolanesandDioxygen 224
6.4.4 HydroacylationofAlkenesUsingNHPIasaPolarityReversal
Catalyst 226
6.4.5 ChiralNHPIDerivativesasEnantioselectiveCatalysts:Kinetic
ResolutionofOxazolidines 228
6.5 Conclusions 229
References 230
7 Ruthenium-CatalyzedOxidationforOrganicSynthesis 241
Shun-IchiMurahashiandNaruyoshiKomiya
7.1 Introduction 241
7.2 RuO -PromotedOxidation 241
4
7.3 OxidationwithLow-ValentRutheniumCatalystsandOxidants 245
7.3.1 OxidationofAlkenes 245
7.3.2 OxidationofAlcohols 249
7.3.3 OxidationofAmines 255
7.3.4 OxidationofAmidesandb-Lactams 260
7.3.5 OxidationofPhenols 262
7.3.6 OxidationofHydrocarbons 265
References 268
8 SelectiveOxidationofAminesandSulfides 277
Jan-E.Bäckvall
8.1 Introduction 277
8.2 OxidationofSulfidestoSulfoxides 277
8.2.1 StoichiometricReactions 278
8.2.1.1 Peracids 278
8.2.1.2 Dioxiranes 278
8.2.1.3 OxoneandDerivatives 279
8.2.1.4 H O in‘‘FluorousPhase’’andRelatedReactions 279
2 2
8.2.2 ChemocatalyticReactions 280
8.2.2.1 H O asTerminalOxidant 280
2 2
8.2.2.2 MolecularOxygenasTerminalOxidant 293
8.2.2.3 AlkylHydroperoxidesasTerminalOxidant 295
8.2.2.4 OtherOxidantsinCatalyticReactions 297
8.2.3 BiocatalyticReactions 297
8.2.3.1 Peroxidases 298
8.2.3.2 KetoneMonooxygenases 299
8.3 OxidationofTertiaryAminestoN-Oxides 300
8.3.1 StoichiometricReactions 300
8.3.2 ChemocatalyticOxidations 302