Modern Methods in Stereoselective Aldol Reactions

544 Pages·2013·5.1 MB·English

by  Rainer Mahrwald (Ed.)

Editedby
RainerMahrwald
ModernMethodsinStereoselectiveAldol
Reactions
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Edited by Rainer Mahrwald
Modern Methods in Stereoselective Aldol
Reactions
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V
Contents
Preface XI
ListofContributors XIII
1 StereoselectiveAcetateAldolReactions 1
PedroRomeaandFe`lixUrp´ı
1.1 Introduction 1
1.2 MukaiyamaAldolReaction 2
1.2.1 ConceptandMechanism 2
1.2.2 ChiralAuxiliaries 4
1.2.3 ChiralMethylKetones 6
1.2.4 ChiralAldehydes 8
1.2.4.1 1,2-AsymmetricInduction 8
1.2.4.2 1,3-AsymmetricInduction 13
1.2.4.3 Merged1,2-and1,3-AsymmetricInduction 17
1.2.5 ChiralLewisAcids 22
1.2.6 ChiralLewisBases 35
1.3 MetalEnolates 41
1.3.1 ConceptandMechanism 41
1.3.2 ChiralAuxiliaries 42
1.3.3 StoichiometricLewisAcids 47
1.3.4 CatalyticLewisAcids 48
1.3.5 ChiralAldehydes 50
1.3.6 ChiralMethylKetones 55
1.3.6.1 α-MethylKetones 56
1.3.6.2 α-HydroxyKetones 57
1.3.6.3 β-HydroxyKetones 60
1.3.6.4 β-Hydroxyα-MethylKetones 63
1.3.6.5 α,β-DihydroxyKetones 64
1.3.6.6 RemoteStereocontrol 67
1.4 Conclusions 68
References 69
VI Contents
2 TheVinylogousMukaiyamaAldolReactioninNaturalProduct
Synthesis 83
MartinCordesandMarkusKalesse
2.1 Introduction 83
2.2 Aldehyde-DerivedSilylDienolEthers 84
2.2.1 Aldehyde-DerivedSilylDienolEthers – Diastereoselective
Processes 84
2.2.2 Aldehyde-DerivedSilylDienolEthers – EnantioselectiveProcesses 87
2.3 Ester-DerivedSilylDienolEthers 90
2.3.1 Ester-DerivedSilylDienolEthers – DiastereoselectiveProcesses 90
2.3.2 Ester-DerivedSilylDienolEthers – EnantioselectiveProcesses 96
2.3.3 Ester-DerivedSilylDienolEthers – Enantioselectiveand
Substrate-ControlledProcesses 105
2.4 Amide-DerivedSilylDienolEthers–VinylketeneSilylN,O-Acetals 108
2.4.1 ModelSystems – Kobayashi’sPioneeringStudies 108
2.4.2 TotalSyntheses 109
2.5 AcyclicAcetoacetate-DerivedSilylDienolates – Chan’sDiene 117
2.5.1 Chan’sDieneinDiastereoselectiveProcesses 117
2.5.2 Chan’sDieneinEnantioselectiveProcesses 121
2.5.3 Chan’sDieneinEnantioselectiveandSubstrate-Controlled
Processes 122
2.6 CyclicAcetoacetate-DerivedDienolates 124
2.6.1 CyclicAcetoacetate-DerivedDienolates – Diastereoselective
Processes 124
2.6.2 CyclicAcetoacetate-DerivedDienolates – Enantioselective
Processes 126
2.6.3 CyclicAcetoacetate-DerivedDienolates – Enantioselectiveand
Substrate-ControlledProcesses 132
2.7 Furan-DerivedSilyloxyDienes 133
2.7.1 Furan-DerivedSilyloxyDienes – DiastereoselectiveProcesses 133
2.7.2 Furan-DerivedSilyloxyDienes – EnantioselectiveProcesses 138
2.7.3 Furan-DerivedSilyloxyDienes – Enantioselectiveand
Substrate-ControlledProcesses 141
2.8 Pyrrole-Based2-SilyloxyDienes 142
2.9 ComparisonwithOtherMethods 148
References 151
3 OrganocatalyzedAldolReactions 155
GabrielaGuillena
3.1 Introduction 155
3.2 ProlineasOrganocatalyst 156
3.2.1 IntramolecularReactions 156
3.2.1.1 IntramolecularProposedMechanism 159
3.2.1.2 ApplicationtoNaturalProductSynthesis 161
3.2.2 IntermolecularReactions 163
Contents VII
3.2.2.1 KetonesasSourceofNucleophile 163
3.2.2.2 AldehydesasSourceofNucleophile 171
3.2.2.3 IntermolecularReactionMechanism 175
3.2.2.4 ApplicationtoNaturalProductSynthesis 177
3.3 ProlineDerivativesasOrganocatalysts 179
3.3.1 ProlinamideDerivatives 180
3.3.1.1 KetonesasSourceofNucleophile 180
3.3.1.2 AldehydesasSourceofNucleophile 197
3.3.1.3 ApplicationtoNaturalProductSynthesis 197
3.3.2 ProlinePeptideDerivatives 199
3.3.2.1 KetonesasSourceofNucleophile 199
3.3.3 HydroxyprolineDerivatives 205
3.3.3.1 IntramolecularReactions 205
3.3.3.2 IntermolecularReactions 207
3.3.4 SulfonimideProlineDerivatives 216
3.3.4.1 KetonesasSourceofNucleophile 216
3.3.4.2 ApplicationtoNaturalProductSynthesis 219
3.3.5 OtherProlineDerivatives 220
3.3.5.1 IntramolecularReactions 220
3.3.5.2 IntermolecularReactions 221
3.3.5.3 ApplicationtoNaturalProductSynthesis 231
3.3.6 OtherOrganocatalysts 233
3.3.6.1 IntramolecularReactions 233
3.3.6.2 IntermolecularReactions 235
3.3.7 Phase-TransferCatalysis 251
3.4 ConclusionsandOutlook 253
References 253
4 SupersilylProtectiveGroupsinAldolReactions 269
PatrickB.BradyandHisashiYamamoto
4.1 Introduction 269
4.2 AldolAdditionwithAcetaldehyde-DerivedSuperSilylEnol
Ether(1) 270
4.3 α-SubstitutedSilylEnolEthersDerivedfromAldehydes 270
4.4 AldolAdditiontoChiralAldehydes 272
4.5 One-PotSequentialAldolReactions 274
4.6 SequentialAldol–AldolReactionsofAcetaldehyde 275
4.6.1 AcetaldehydeDoubleAldolReactions 275
4.6.2 AcetaldehydeTripleAldolReactions 275
4.6.3 MixedSequentialAldol–AldolReactions 277
4.7 DoubleAldolReactionswithα-SubstitutedSilylEnolEthers 277
4.7.1 SequentialAldol–AldolReactionswithMixedSEEs 277
4.7.2 PropionaldehydeAldol–AldolCascadeReactions 279
4.7.3 HaloacetaldehydeAldol–AldolCascades 280
4.8 StereochemicalConsiderations 281
VIII Contents
4.9 AldolReactionsofβ-SupersiloxyMethylKetones 282
4.10 TotalSynthesisofNaturalProductsUsingSupersilylAldol
Reactions 285
4.11 ConclusionandOutlook 288
References 288
5 AsymmetricInductioninAldolAdditions 293
LuizC.Dias,EllenC.Polo,Em´ılioC.deLuccaJr,andMarcoA.B.Ferreira
5.1 Introduction 293
5.2 AsymmetricInductionUsingChiralKetones 295
5.2.1 1,4-AsymmetricInductionUsingα-AlkylKetones 296
5.2.2 1,4-AsymmetricInductionUsingα-Methyl-β-BranchedKetones 302
5.2.3 1,4-AsymmetricInductionUsingα-AlkoxyKetones 305
5.2.4 1,5-AsymmetricInductionUsingβ-AlkoxyMethylKetones 313
5.2.5 1,6-AsymmetricInductionUsingChiralMethylKetones 317
5.3 AsymmetricInductionUsingChiralAldehydes 317
5.3.1 1,2-AsymmetricInductionUsingChiralAldehydes 317
5.3.2 1,3-AsymmetricInductionUsingChiralAldehydes 335
5.3.3 AsymmetricInductionUsingα-Methyl-β-AlkoxyAldehydes 342
5.3.4 AsymmetricInductionUsingα,β-BisalkoxyAldehydes 357
5.4 AsymmetricInductionintheAldolAdditionofChiralEnolatestoChiral
Aldehydes 360
References 371
6 PolypropionateSynthesisviaSubstrate-ControlledStereoselectiveAldol
CouplingsofChiralFragments 377
DaleE.Ward
6.1 Introduction 377
6.2 PrinciplesofStereoselectiveAldolReactions 378
6.2.1 RelativeTopicity 378
6.2.2 ChiralReactants 381
6.2.2.1 DiastereofaceSelectivityofChiralEthylKetones 381
6.2.2.2 DiastereofaceSelectivityofChiralAldehydes 386
6.2.2.3 MultiplicativityRule 394
6.3 StereoselectiveAldolCouplingofChiralReactants 398
6.3.1 2-Alkoxy-1-MethylethylEthylKetones:Paterson’sDipropionate
Equivalent 398
6.3.1.1 ReactionswithAchiralAldehydes 398
6.3.1.2 ReactionswithChiralAldehydes 400
6.3.2 1-MethylalkylEthylKetones:3-DeoxyPolypropionateEquivalents 402
6.4 2-AlkoxyalkylEthylKetones:2-DesmethylPolypropionate
Equivalents 406
6.4.1 2-Alkoxy-1-MethylalkylEthylKetones:PolypropionateEquivalents 409
6.4.1.1 (E)BoronEnolates 411
6.4.1.2 (Z)BoronEnolates 412
Contents IX
6.4.1.3 SilylEnolates 413
6.4.1.4 LithiumEnolates 414
6.4.1.5 TitaniumEnolates 416
6.4.1.6 TinEnolates 419
6.5 Conclusions 420
References 424
7 ApplicationofOxazolidinethionesandThiazolidinethionesinAldol
Additions 431
MichaelT.Crimmins
7.1 Introduction 431
7.2 PreparationofOxazolidinethioneandThiazolidinethioneChiral
Auxiliaries 431
7.3 AcylationofOxazolidinethioneandThiazolidinethioneChiral
Auxiliaries 433
7.4 PropionateAldolAdditions 434
7.5 AcetateAldolAdditions 437
7.6 GlycolateAldolAdditions 443
7.6.1 SyntheticApplicationsofAldolAdditionsof N-Propionyl
OxazolidinethionesandThiazolidinethionesandTheirSubstituted
Variants 443
7.6.2 SyntheticApplicationsofAldolAdditionsof N-Acetyloxazolidinethiones
andThiazolidinethiones 461
7.6.3 SyntheticApplicationsofanti-AldolAdditionsof
N-Glycolyloxazolidinethiones 466
References 471
8 Enzyme-CatalyzedAldolAdditions 475
PereClape´sandJesu´sJoglar
8.1 Introduction 475
8.2 PyruvateAldolases 477
8.3 N-AcetylneuraminicAcidAldolase(NeuA) 478
8.3.1 NovelNeuABiocatalystbyProteinEngineering 482
8.3.2 Large-ScaleProcess 486
8.3.3 RelatedPyruvateAldolases/2-OxobutyrateAldolases 487
8.4 DihydroxyacetonePhosphate(DHAP)Aldolases 494
8.4.1 StructureandMechanism 500
8.4.2 L-Rhamnulose-1-PhosphateAldolaseasaDHA-Dependent
Aldolase 502
8.5 D-Fructose-6-PhosphateAldolaseandTransaldolaseBPhe178Tyr:
FSA-LikeAldolases 503
8.6 2-Deoxy-D-Ribose-5-PhosphateAldolase(RibAorDERA;EC
4.1.2.4) 510
8.7 Glycine/AlanineAldolases 514
8.8 AldolReactionsCatalyzedbyNonaldolases 520
X Contents
8.9 ConclusionsandPerspectives 520
8.9.1 SubstrateTolerance/Stereoselectivity 521
8.9.2 FuturePerspectives 521
References 522
Index 529