Organic Stereochemistry: Experimental and Computational Methods

337 Pages·2015·3.501 MB·English

by  Hua-Jie Zhu

Hua-JieZhu
OrganicStereochemistry
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Organic Stereochemistry
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V
Contents
Preface IX
Acknowledgments XI
ListofAbbreviations XIII
PartI Fundamentals 1
1 Chirality 3
1.1 Introduction 3
1.2 TetrahedronofCarbon 9
1.2.1 Terpenoids 9
1.2.2 Flavonoids 13
1.2.3 Alkaloids 14
1.2.4 Steroids 16
1.2.5 Glycosides 17
1.2.6 Others 18
1.3 OtherStereogenicCenters 19
1.4 OpticalCharacteristics 23
1.4.1 MeasurementofOR 24
1.4.2 ECDandItsDefinition 25
1.4.3 OutlineofVCD 26
1.4.4 OutlineofROA 27
References 28
2 Non-opticalMethodinConfigurationStudy 31
2.1 13CNMRSpectra 31
2.1.1 NMRandAtomicStructure 31
2.1.2 13CNMRCalculation 32
2.1.3 1HNMR 34
2.1.4 13CNMRPredictionandConformationalSearch 34
2.2 X-RayDiffractionandMosherMethod 41
2.2.1 X-RayDiffraction 41
2.2.2 MosherMethod 44
2.3 TransitionStateEnergyandChiralitySelectivity 51
VI Contents
2.4 SeparationofChiralCompounds 53
2.4.1 ChiralOrganicBases 53
2.4.2 ChiralOrganicAcids 53
2.4.3 ChiralOrganicAlcohols 53
2.4.4 Others 54
References 55
PartII Techniques 57
3 OpticalRotation(RotatoryDispersion,ORD) 59
3.1 Introduction 59
3.2 QuantumTheory 59
3.3 MatrixModel 63
3.3.1 MatrixBasis 65
3.3.2 ExplanationofGeneralORCharacteristics 68
3.3.2.1 SampleCalculations 68
3.3.2.2 CalculatedValuesinSameSeriesofCompounds 73
3.4 ORD 77
3.5 Application 77
3.5.1 ACAssignmentforMono-StereogenicCenterCompounds 79
3.5.2 MatrixModelApplication 80
3.5.3 ACAssignmentforPoly-StereogenicCenterCompounds 82
3.5.4 UsingORDMethod 83
References 84
4 ElectronicCircularDichroism 87
4.1 ExcitonChiralityCD 87
4.2 ECDCharacteristicsforChiralMetallicCompounds 92
4.3 QuantumTheoryBasis 94
4.4 PrincipleUsingECD 95
4.5 Application 97
4.5.1 ProceduretoDoECD 97
4.5.2 ECDApplication 97
4.5.3 UVCorrection 102
References 105
5 VibrationalCircularDichroismandRamanOpticalActivity 107
5.1 ExcitonChirality 108
5.2 QuantumTheoryBasis 109
5.2.1 VCDandIR 109
5.2.2 ROAandRamanScattering 110
5.3 PrinciplesUsingVCDandROA 113
5.4 Application 115
5.4.1 VCDApplication 115
Contents VII
5.4.2 ROAApplication 124
References 126
6 CombinationalUseofDifferentMethods 129
6.1 TacticstoSelectMethods 129
6.1.1 13CNMRMethods 130
6.1.2 ORandORD 131
6.1.3 Matrix 132
6.1.4 ECD 132
6.1.5 VCDMethod 133
6.2 ExamplesandDiscussion 133
6.3 RevisedStructures 138
6.3.1 ORDMethod 139
6.3.2 CombinationalUseofORandECD 144
6.3.3 VCDandECD 146
6.3.4 ComprehensiveUseofOR,ECD,andVCD 147
References 160
PartIII Reactions 163
7 EnantioselectiveReaction 165
7.1 EnantioselectiveAddition 165
7.1.1 OrganicZn-orZn-TiReagent 165
7.1.2 OrganicCu–Zn,Cu–LiReagent 169
7.1.3 Organo-FeComplexes 173
7.1.4 OtherOrgano-MetallicComplexes 175
7.1.5 Organo-SiReagents 178
7.2 EnantioselectiveReduction 178
7.2.1 GreenChemistry 181
7.3 EnantioselectiveOxidation 184
7.4 PredictionofeeUsingCalculations 185
7.5 CatalystTypes 189
7.5.1 AminoAlcohols 189
7.5.2 ChiralLigandsContainingN–OGroup 190
7.5.3 ChiralAxialCatalysts 191
7.5.4 Solid-SupportedChiralCompounds 192
7.5.5 SpiralChiralCompounds 193
7.5.6 Asymmetric-Axle-SupportedChiralCatalyst 194
7.5.7 ChiralShiff-BaseLigands 195
7.5.8 SomeAsymmetricLewisAcids 196
7.5.9 OrganicP-ContainingLigands 197
7.6 ThreePhenomena 198
7.6.1 ChiralityAmplification(NonlinearEffect) 198
7.6.2 Auto-SelfCatalysis 199
VIII Contents
7.6.3 Odd–EvenCarbonEffect 199
References 201
8 ChemoselectiveReaction 205
8.1 ChemoselectiveAdditions 205
8.1.1 AdditiontoC=OorC=CGroups 205
8.2 ChemoselectiveReduction 210
8.3 ChemoselectiveOxidation 225
8.4 OtherChemoselectiveReactions 231
References 237
9 StereoselectiveReaction 241
9.1 ConformationalStudy 241
9.2 EffectofConformationonReactions 247
9.3 RegioselectiveReactions 251
9.4 DiastereoselectiveReactions 260
9.4.1 DiastereoselectiveAdditions 260
9.4.2 OtherDiastereoselectiveReactions 270
9.5 CalculationUsingTheoreticalProtocol 272
References 277
10 TotalOrganicSynthesis 279
10.1 Introduction 279
10.2 RetrosynthesisStrategies 279
10.3 ExamplesinSynthesis 285
10.3.1 (+)-Hirsutene 285
10.3.2 (2R,3S)-RubiginoneA andItsAnalog 287
2
10.3.3 (+)-BrefeldinA 290
10.3.4 MalyngamideUandItsACReassignment 292
10.3.5 TaxolDerivatives 296
10.3.6 AmphidinolideT2andItsDerivatives 298
10.3.7 (+)-Vindoline 303
10.4 CalculationinTotalSynthesis 306
References 309
Index 313