Modern Oxidation Methods, Second Edition

473 Pages·2010·4.64 MB·English

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
ModernOxidationMethods.EditedbyJan-ErlingBäckvall
Copyright(cid:1)2010WILEY-VCHVerlagGmbH&Co.KGaA,Weinheim
ISBN:978-3-527-32320-3
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
Contents IX
8.3.3 BiocatalyticOxidation 306
8.3.4 ApplicationsofAmineN-OxidationinCoupled
CatalyticProcesses 306
8.4 ConcludingRemarks 308
References 309
9 LiquidPhaseOxidationReactionsCatalyzedbyPolyoxometalates 315
RonnyNeumann
9.1 Introduction 315
9.2 Polyoxometalates(POMs) 316
9.3 OxidationwithMono-OxygenDonors 317
9.4 OxidationwithPeroxygenCompounds 323
9.5 OxidationwithMolecularOxygen 331
9.6 HeterogenizationofHomogeneousReactions–Solid-Liquid,
Liquid-Liquid,andAlternativeReactionSystems 341
9.6.1 Solid-LiquidReactions 341
9.6.2 Liquid-LiquidReactionsandReactionsin‘Alternative’Media 343
9.7 Conclusion 346
References 346
10 OxidationofCarbonylCompounds 353
EricV.JohnstonandJan-E.Bäckvall
10.1 Introduction 353
10.2 OxidationofAldehydestoCarboxylicAcids 353
10.2.1 Metal-FreeOxidationofAldehydestoCarboxylicAcids 354
10.2.2 Metal-CatalyzedOxidationofAldehydestoCarboxylicAcids 355
10.3 OxidationofKetones 356
10.3.1 Baeyer-VilligerReactions 356
10.3.2 CatalyticAsymmetricBaeyer-VilligerReactions 356
10.3.2.1 ChemocatalyticVersions 357
10.3.2.2 BiocatalyticVersions 358
References 365
11 Manganese-CatalyzedOxidationwithHydrogenPeroxide 371
WesleyR.Browne,JohannesW.deBoer,DirkPijper,JelleBrinksma,
RonaldHage,andBenL.Feringa
11.1 Introduction 371
11.2 Bio-inspiredManganeseOxidationCatalysts 372
11.3 Manganese-CatalyzedBleaching 375
11.4 Epoxidationandcis-DihydroxylationofAlkenes 375
11.4.1 ManganeseSalts 376
11.4.2 Porphyrin-BasedCatalysis 378
11.4.3 Salen-BasedSystems 381
11.4.4 Tri-andTetra-azacycloalkaneDerivatives 385
11.4.4.1 Tetra-azacycloalkaneDerivatives 386
11.4.4.2 TriazacyclononaneDerivatives 387
X Contents
11.4.4.3 ManganeseComplexesforAlkeneOxidationBased
onPyridylLigands 403
11.5 ManganeseCatalystsfortheOxidationofAlkanes,Alcohols,
andAldehydes 406
11.5.1 OxidationofAlkanes 406
11.5.2 OxidationofAlcoholsandAldehydes 407
11.5.3 Sulfides,Sulfoxides,andSulfones 408
11.6 Conclusions 411
References 412
12 BiooxidationwithCytochromeP450Monooxygenases 421
MarcoGirhardandVladaB.Urlacher
12.1 Introduction 421
12.2 PropertiesofCytochromeP450Monooxygenases 422
12.2.1 Structure 422
12.2.2 Enzymology 423
12.2.3 ReactionsCatalyzedbyP450s 425
12.2.4 P450sasIndustrialBiocatalysts 429
12.2.4.1 Advantages 429
12.2.4.2 ChallengesintheDevelopmentofTechnicalP450Applications 429
12.2.4.3 GeneralAspectsofIndustrialApplicationandEngineering
ofP450s 430
12.3 ApplicationandEngineeringofP450sforthePharmaceutical
Industry 430
12.3.1 MicrobialOxidationswithP450sforSynthesis
ofPharmaceuticals 431
12.3.2 ApplicationofMammalianP450sforDrugDevelopment 434
12.3.2.1 EnhancementofRecombinantExpressioninE.coli 435
12.3.2.2 EnhancementofActivityandSelectivityandEngineeringof
NovelActivities 436
12.3.2.3 ConstructionofArtificialSelf-SufficientFusionProteins 436
12.4 ApplicationofP450sforSynthesisofFineChemicals 437
12.5 EngineeringofP450sforBiocatalysis 438
12.5.1 CofactorSubstitutionandRegeneration 438
12.5.1.1 CofactorSubstitutionInVitro 438
12.5.1.2 CofactorRegenerationInVitro 439
12.5.1.3 CofactorRegenerationinWhole-Cells 439
12.5.2 ConstructionofArtificialFusionProteins 440
12.5.3 EngineeringofNewSubstrateSpecificities 440
12.5.3.1 P450 fromPseudomonasputida 440
cam
12.5.3.2 P450 fromBacillusmegaterium 442
BM3
12.6 FutureTrends 443
References 444
Index 451