Asymmetric Organic Synthesis with Enzymes

342 Pages·2008·2.699 MB·English

by  Cotor V., Alfonso I., Garcia-Urdiales E. (eds.)

Asymmetric Organic Synthesis with Enzymes
Edited by
Vicente Gotor, Ignacio Alfonso, and Eduardo García-Urdiales

Asymmetric Organic Synthesis
with Enzymes
Edited by
Vicente Gotor, Ignacio Alfonso, and
Eduardo Garc´ıa-Urdiales
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Asymmetric Organic Synthesis with Enzymes
Edited by
Vicente Gotor, Ignacio Alfonso, and Eduardo García-Urdiales
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V
Contents
Preface X1
List of Contributors XIII
I Methodology 1
1 MediumEngineering 3
GiacomoCarreaandSergioRiva
1.1 Introduction 3
1.2 ModulationofEnzymeEnantioselectivitybyMedium
Engineering 5
1.2.1 SelectivityEnhancementbyAdditionofWater-Miscible
OrganicCosolvents 5
1.2.2 SelectivityEnhancementinOrganicMediawithLowWater
Activity 7
1.2.2.1 OrganicSolventSystems 7
1.2.2.2 EnzymePropertiesinOrganicSolvents 8
1.2.2.3 MediumEngineering 9
1.2.3 Rationales 12
1.2.4 ModulationofEnzymeSelectivity:NewTrendsofResearch 14
1.2.4.1 IonicLiquids 14
1.2.4.2 Additives 16
1.3 ConclusionsandOutlooks 17
References 17
2 DirectedEvolutionasaMeanstoEngineerEnantioselective
Enzymes 21
ManfredT.Reetz
2.1 Introduction 21
2.2 MolecularBiologicalMethodsforMutagenesis 23
2.3 High-throughputScreeningMethodsforEnantioselectivity 27
VI Contents
2.4 ExamplesofEnhancingtheEnantioselectivityofEnzymesby
DirectedEvolution 28
2.4.1 LipasefromPseudomonasaeruginosa(PAL) 28
2.4.2 OtherLipases 38
2.4.3 Esterases 38
2.4.4 Hydantoinases 39
2.4.5 Nitrilases 39
2.4.6 EpoxideHydrolases 41
2.4.7 Phosphotriesterases 45
2.4.8 Aminotransferases 45
2.4.9 Aldolases 46
2.4.10 CyclohexanoneandCyclopentanoneMonooxygenasesas
Baeyer–VilligerasesandSulfoxidationCatalysts 48
2.4.11 MonoamineOxidases 54
2.4.12 CytochromeP450Enzymes 55
2.4.13 OtherEnzymes 55
2.5 ConclusionsandPerspectives 56
References 56
3 TheSearchforNewEnzymes 65
Jean-LouisReymondandWolfgangStreit
3.1 Introduction 65
3.2 Mechanism-basedEnzymeDesign 66
3.2.1 CatalyticAntibodies 66
3.2.2 RationalDesignofNewCatalystsonEnzymeandProteinBasis 69
3.2.3 SyntheticEnzymeModels 71
3.3 Metagenomics 71
3.3.1 ConstructionofMetagenome-derivedDNALibraries 72
3.3.1.1 SelectionoftheEnvironment 72
3.3.1.2 CloningStrategies 73
3.3.1.3 ScreeningandDetectionTechnologies 73
3.3.1.4 MajorProblemsthatNeedtobeAddressed 74
3.3.2 TheGenomesofNotYetCulturedMicrobesasResources
forNovelGenes 75
3.3.2.1 PolysaccharideDegrading/ModifyingEnzymes 75
3.3.2.2 LipolyticBiocatalysts 77
3.3.2.3 VitaminBiosynthesis 77
3.3.2.4 Nitrilases,NitrileHydratases,andAmidases 78
3.3.2.5 Oxidoreductases/Dehydrogenases 79
3.3.2.6 Proteases 79
3.3.2.7 GlycerolHydratases 79
3.3.2.8 AntibioticsandPharmaceuticals 79
3.4 Conclusion 80
References 80
Contents VII
II SyntheticApplications 87
4 DynamicKineticResolutions 89
BelénMartín-MatuteandJan-E.Bäckvall
4.1 Introduction 89
4.1.1 SynthesisofEnantiomericallyPureCompounds 89
4.1.2 KineticResolution(KR)andDynamicKinetic
Resolution(DKR) 90
4.1.3 EnzymesinOrganicChemistry 91
4.2 Metal-CatalyzedRacemization 92
4.2.1 DKRofAllylicAcetatesandAllylicAlcohols 93
4.2.2 DKRofsec-alcohols 94
4.2.3 DKRofAmines 98
4.3 Base-CatalyzedRacemization 98
4.3.1 DKRofThioesters 99
4.3.2 DKRofActivatedEsters 100
4.3.3 DKRofOxazolones 100
4.3.4 DKRofHydantoins 101
4.3.5 DKRofAcyloins 101
4.4 Acid-CatalyzedRacemization 101
4.5 RacemizationthroughContinuousReversibleFormation–Cleavage
oftheSubstrate 102
4.5.1 DKRofCyanohydrins 103
4.5.2 DKRofHemithioathetals 103
4.6 RacemizationCatalyzedbyAldehydes 104
4.7 Enzyme-CatalyzedRacemization 106
4.8 RacemizationthroughS 2Displacement 106
N
4.9 OtherRacemizationMethods 107
4.9.1 DKRof5-Hydroxy-2-(5H)-Furanones 107
4.9.2 DKRofHemiaminals 107
4.9.3 DKRof 8-Amino-5,6,7,8-tetrahydroquinoline 108
4.10 ConcludingRemarks 109
References 110
5 DeracemizationandEnantioconvergentProcesses 115
NicholasJ.Turner
5.1 Introduction 115
5.2 DeracemizationProcesses 116
5.2.1 CyclicOxidation–ReductionSystems 116
5.2.2 MicrobialDeracemizationofSecondaryAlcoholsUsingaSingle
Microorganism 122
5.2.3 DeracemizationofAlcoholsUsingTwoEnzyme/Microorganism
Systems 124
5.2.4 Epoxides 126