Innovative Catalysis in Organic Synthesis: Oxidation, Hydrogenation, and C-X Bond Forming Reactions

360 Pages·2012·3.91 MB·English

by  Pher G. Andersson

Editedby
PherG.Andersson
InnovativeCatalysisinOrganicSynthesis
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Edited by Pher G. Andersson
Innovative Catalysis in Organic Synthesis
Oxidation, Hydrogenation,
and C–X Bond Forming Reactions
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V
Contents
Foreword XI
ListofContributors XIII
PartI OxidationReactions 1
1 PolyoxometalatesasHomogeneousOxidationCatalysts 3
MauroCarraro,AndreaSartorel,MasoomaIbrahim,NadeenNsouli,
ClaireJahier,SylvainNlate,UlrichKortz,andMarcellaBonchio
1.1 SolubleMetalOxidesasOxidationCatalysts 3
1.2 HomogeneousOxidationswithPOMsBasedOnlyonMo(VI),W(VI),
V(V)AddendaIons 6
1.2.1 OxidationwithHydrogenPeroxideby
Peroxopolyoxotungstates-Dendrimers 8
1.2.2 HomogeneousOxidationwithHydrogenPeroxideinthePresenceof
VacantandHybridPOMs 10
1.3 HomogeneousOxidationswithTMS-POMs 12
1.3.1 PeroxopolyoxometalatesofHf/Zr 13
1.3.2 AerobicOxidationswithPolyoxopalladates 16
1.3.3 TMSPsasOxygen-EvolvingCatalysts 17
1.4 Conclusions 19
Acknowledgments 19
References 20
2 BioinspiredOxidationsCatalyzedbyNonhemeIronandManganese
Complexes 27
IsaacGarcia-Bosch,IrenePrat,XaviRibas,andMiquelCostas
2.1 Introduction 27
2.2 CatalyticOxidationofC=CBondsbyNonhemeIronandManganese
Complexes 27
2.2.1 Epoxidation 27
2.2.1.1 Iron-BasedCatalysts 27
2.2.1.2 Manganese-BasedCatalysts 30
2.2.2 cis-Dihydroxylation 34
VI Contents
2.2.2.1 Iron-BasedCatalysts 34
2.2.2.2 Manganese-BasedCatalysts 37
2.3 CatalyticOxidationofC–HBondsbyNonhemeIronandManganese
Complexes 38
2.3.1 Hydroxylation 38
2.3.1.1 Iron-BasedCatalysts 38
2.3.1.2 Manganese-BasedCatalysts 40
2.3.2 Desaturation 41
2.3.2.1 Iron-BasedCatalysts 41
2.3.2.2 Manganese-BasedCatalysts 42
References 43
3 TheFabulousDestinyofSulfenicAcids 47
MariaChiaraAversa,PaolaBonaccorsi,DavidMadec,GuillaumePrestat,
andGiovanniPoli
3.1 Introduction 47
3.2 SynthesisofStableSulfenicAcids 48
3.3 GenerationofTransientSulfenicAcids 52
3.4 ReactivityofSulfenicAcidsinthePreparationofSulfoxidesand
UnsymmetricalDisulfides 57
3.5 SynthesisofStableSulfenateAnions 62
3.6 GenerationofTransientSulfenateAnionsLeadingtoSulfoxides 65
3.7 Conclusions 73
References 73
4 SustainableCatalyticOxidationswithPeroxides 77
IsabelW.C.E.Arends,ValeriaConte,andGiuliaLicini
4.1 Introduction 77
4.2 Metal-BasedSelectiveOxidations 78
4.2.1 BrominationReactions 78
4.2.2 OxidationofNitrogen-ContainingSubstrates 85
4.2.3 OxidationofSulfur-ContainingSubstrates 85
4.2.4 OxidationofAlkenes 89
4.3 BiocatalyticOxidationswithHydrogenPeroxide 92
4.3.1 WhyEnzymesandHOOH? 92
4.3.2 BiocatalyticSulfoxidation 95
4.3.3 BiocatalyticAlkenesEpoxidation 96
4.3.4 BiocatalyticAlcoholsOxidation 98
4.4 Conclusions 99
Acknowledgments 99
References 100
Contents VII
PartII HydrogenationandReductionReactions 103
5 AsymmetricHydrogenationofDehydroaminoacidDerivativesby
Rh-CatalystswithChiralMonodentateP-Ligands 105
SerafinoGladiali,ElisabettaAlberico,andIlyaGridnev
5.1 Introduction 105
5.2 ChiralMonodentatePhosphorusLigandsinAsymmetric
Hydrogenation 108
5.3 CatalystPrecursors 112
5.4 MechanisticInsights 117
5.5 FormationoftheMACAdducts 121
5.6 EvolutionofMAC-AdductsandOriginofEnantioselection 124
References 126
6 RecentAdvancesintheSynthesisandCatalyticHydrogenationof
DehydroaminoAcidDerivativesandBicyclo[2.2.2]octenes 131
Ve´roniqueMichelet,VirginieRatovelomanana-Vidal,VasileI.Paˆrvulescu,
andMarijanKocˇevar
6.1 Introduction 131
6.2 SynthesisofDDAADerivativesandBicyclo[2.2.2]octenes 133
6.3 Ligands 133
6.4 HomogeneousHydrogenationandHydrogenolysisReactionswith
DehydroaminoAcidDerivativesandBicyclo[2.2.2]oct-7-enesover
Nanocolloids-ModifiedCatalysts 136
6.4.1 NanometalColloids-ModifiedCatalysts 136
6.4.2 NanooxideColloids-ModifiedCatalysts 140
6.5 HeterogeneousCatalystsforHydrogenolysisof
Bicyclo[2.2.2]oct-7-enes 142
6.5.1 HeterogeneizedLigand-ModifiedNanoclusters 142
6.6 Layered-DoubleHydroxidesasaSupportforRh(TPPTS)3and
Rh-(m-TPPTC)3HomogeneousCatalysts 144
6.7 Conclusions 147
Acknowledgments 147
References 148
7 Ir-CatalyzedHydrogenationofMinimallyFunctionalizedOlefinsUsing
Phosphite–NitrogenLigands 153
MontserratDie´guez,PherG.Andersson,andOscarPa`mies
7.1 Introduction 153
7.2 ApplicationofPhosphite–NitrogenLigands 155
7.3 Conclusions 161
Acknowledgments 163
References 163
VIII Contents
8 ModelinginHomogeneousCatalysis:aTutorial 167
EricClotandPer-OlaNorrby
8.1 Introduction 167
8.2 MolecularModeling 167
8.3 WaveFunctionTheory,WFT 168
8.4 DensityFunctionalTheory,DFT 169
8.5 Orbitals 170
8.6 BasisSets 172
8.7 Solvation 174
8.8 AnalyzingtheReactionEnergies 175
8.9 AnalyzingtheElectronicStructure 177
8.9.1 TheNBOMethod 178
8.9.1.1 HowDoesItWork? 178
8.9.1.2 DeparturefromtheLewisStructure 180
8.9.1.3 NBOandTransitionMetalComplexes 183
8.9.2 TheAIMMethod 187
8.9.2.1 HowDoesItWork? 187
8.9.2.2 NatureoftheBondedInteraction 189
References 190
PartIII C–CandC–HeteroBond-FormingReactions 193
9 GoldenTimesforAllenes 195
NorbertKrause
9.1 Introduction 195
9.2 CyclizationofHydroxyallenes 196
9.3 CyclizationofAminoallenes 203
9.4 CyclizationofThioallenes 206
9.5 Conclusion 206
References 207
10 CopperCatalysisinAreneandHeteroareneFunctionalizationthrough
C–HBondActivation 211
SandroCacchi,GiancarloFabrizi,andAntonellaGoggiamani
10.1 Introduction 211
10.2 C–CBond-FormingReactions 212
10.2.1 Via(Hetero)aryl-H/R-XCoupling 212
10.2.1.1 R–X=(Hetero)arylHalides 212
10.2.1.2 R–X=AlkenylBromides 215
10.2.1.3 R–X=BrCH Ar 216
2
10.2.2 Via(Hetero)aryl-H/Ar I+X−Coupling 217
2
10.2.2.1 Direct(Hetero)arylationofHeteroarenes 217
10.2.2.2 DirectArylationofArenes 218
10.2.3 Via(Hetero)aryl-H/C–HCoupling 219
10.2.3.1 Dimerizationof(Hetero)arenes 219
Contents IX
10.2.3.2 CyclizationofAnilides 220
10.2.3.3 CyclizationofN-arylβ-Enaminones 221
10.2.4 ViaAryl-HAdditiontoTerminalAlkynes 223
10.3 C–NBond-FormingReactions 223
10.4 C–OBond-FormingReactions 227
10.5 C–HalogenBond-FormingReactions 229
References 230
11 LigatedOrganocuprates:anA–ZRoutemapofMechanismand
Application 233
SimonWoodwardandDarrenWillcox
11.1 Introduction 233
11.2 AcceptedMechanisticProposals 233
11.2.1 KineticandNMRStudies 235
11.2.2 ComputationalStudies 242
11.2.3 NonlinearEffects 243
11.2.4 Challenges 245
11.3 SelectiveApplicationsinPrivilegedCopper(I)Catalysis 245
11.3.1 ConjugateAddition 245
11.3.2 AdditionstoAllylicHalides 250
References 252
12 Rh-,Ag-,andCu-CatalyzedC–NBondFormation 257
PhilippeDauban,CamilleLescot,M.MarDiaz-Requejo,and
PedroJ.Perez
12.1 Introduction 257
12.2 HistoricalBackground 258
12.3 Copper-andSilver-CatalyzedC–NBondFormation 260
12.4 Rhodium-CatalyzedC–NBondFormation 265
12.5 Conclusions 273
References 274
13 DevelopmentoftheAsymmetricNozaki–Hiyama–KishiReaction 279
Gra´inneC.HargadenandPatrickJ.Guiry
13.1 Introduction 279
13.2 DevelopmentofaCatalyticNozaki–Hiyama–KishiReaction 279
13.3 CatalyticEnantioselectiveNozaki–Hiyama–KishiReaction 281
13.4 ApplicationofSalen-DerivedLigandsintheEnantioselective
Nozaki–Hiyama–KishiReaction 283
13.5 ApplicationofOxazoline-ContainingLigandsintheCatalytic
EnantioselectiveNozaki–Hiyama–KishiReaction 286
13.6 ApplicationofTetheredBis(8-quinolinato)ChromiumComplexesin
theCatalyticEnantioselectiveNozaki–Hiyama–Kishi 299
13.7 ApplicationofChiralSpirocyclicBorateLigandstotheCatalytic
EnantioselectiveNozaki–Hiyama–KishiAllylation 303
X Contents
13.8 ApplicationsofCatalyticNozaki–Hiyama–KishiReactioninTotal
Synthesis 303
13.9 Conclusions 305
References 306
14 ChiralImidateLigands:SynthesisandApplicationsinAsymmetric
Catalysis 309
TimothyNo¨el,KatrienBert,PieterJanssens,andJohanVanderEycken
14.1 Introduction 309
14.2 CyclicImidates 311
14.3 SynthesisofImidates 312
14.4 SynthesisofImidateLigands 313
14.5 SynthesisofImidate–Copper(I)Complexes 313
14.6 ApplicationofChiralImidateLigandsinEnantioselective
Catalysis 315
14.6.1 Copper(I)-CatalyzedAsymmetricAziridination 315
14.6.2 AsymmetricDiethylzincAddition 316
14.6.3 AsymmetricPalladium(0)-CatalyzedAllylicAlkylations 316
14.6.4 AsymmetricIridium(I)-CatalyzedHydrogenations 318
14.7 NovelSyntheticApplicationsofCyclicImidates 320
14.7.1 One-StepSynthesisofChiralOxazoline–AlcoholLigands 320
14.7.2 SynthesisofChiralspiro-2-Alkoxy-Imidazolidines 321
14.8 Conclusions 322
References 324
15 CatalyzedOrganicReactionsinBallMills 327
AchimStolle,BerndOndruschka,AnkeKrebs,andCarstenBolm
15.1 Introduction 327
15.2 Acid-orBase-CatalyzedReactions 328
15.3 OrganocatalyticMethods 333
15.3.1 AsymmetricAldolReactions 333
15.3.2 CycloadditionandRelatedReactions 335
15.4 Metal-CatalyzedReactions 338
15.4.1 Suzuki–MiyauraReaction 338
15.4.2 Mizoroki–HeckReaction 340
15.4.3 SonogashiraReaction 341
15.4.4 Cu-CatalyzedReactions 343
15.4.5 MiscellaneousMetal-CatalyzedReactions 345
15.5 ConclusionandPerspective 347
References 348
Index 351