C-H Activation for Asymmetric Synthesis

286 Pages·2019·12.493 MB·English

by  Françoise Colobert , Joanna Wencel-Delord

C–HActivationforAsymmetricSynthesis
C–H Activation for Asymmetric Synthesis
Editedby
FrançoiseColobert
JoannaWencel-Delord
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v
Contents
Foreword xi
PartI AsymmetricActivationofC(sp3)—HBonds 1
PartI.A C(sp3)—HBondInsertionbyMetalCarbenoidsand
Nitrenoids 2
1 StereoselectiveC—CBond-FormingReactionsThrough
C(sp3)—HBondInsertionofMetalCarbenoids 3
AoifeM.Buckley,ThomasA.Brouder,AlanFord,andAnitaR.Maguire
1.1 Introduction 3
1.2 DiazoCompounds 4
1.3 MechanisticUnderstanding 5
1.4 Catalysts 7
1.4.1 Copper 7
1.4.1.1 BisoxazolineandSchiffBase 7
1.4.2 Rhodium 8
1.4.2.1 Rhodium(II)Carboxylates 9
1.4.2.2 Rhodium(II)Carboxamidates 10
1.4.2.3 Ortho-metalatedComplexes 11
1.4.3 IridiumandRuthenium 11
1.5 IntramolecularC(sp3)—HBondInsertion 11
1.5.1 Chemoselectivity 13
1.5.1.1 CatalystEffects 13
1.5.1.2 SubstrateEffects 14
1.5.2 Regioselectivity 16
1.5.2.1 FormationofThree-MemberedRings 17
1.5.2.2 FormationofFour-MemberedRings 18
1.5.2.3 FormationofFive-MemberedRings 20
1.5.2.4 FormationofSix-MemberedRings 20
1.5.3 Diastereoselectivity 23
1.5.3.1 SubstrateEffects 23
1.5.3.2 CatalystEffects 25
vi Contents
1.5.4 Enantioselectivity 25
1.6 IntermolecularC(sp3)—HBondInsertion 30
1.6.1 Chemoselectivity 30
1.6.1.1 DiazoCompounds 32
1.6.1.2 CatalystEffects 34
1.6.1.3 SubstrateFunctionalGroups 35
1.6.2 Regioselectivity 36
1.6.2.1 SubstrateEffects 36
1.6.2.2 CatalystEffects 38
1.6.2.3 DiazoCompoundEffects 39
1.6.3 Diastereoselectivity 39
1.6.3.1 SubstrateEffects 39
1.6.3.2 CatalystEffects 42
1.6.4 Enantioselectivity 43
1.7 Conclusion 45
References 45
2 StereoselectiveC—NBond-FormingReactionsThrough
C(sp3)—HBondInsertionofMetalNitrenoids 51
PhilippeDauban,RomainRey-Rodriguez,andAliNasrallah
2.1 Introduction 51
2.2 HistoricalBackground 52
2.2.1 SeminalStudiesinCatalyticC(sp3)–HAmination 52
2.2.2 MechanisticandStereochemicalIssues 56
2.3 CatalyticStereoselectiveC(sp3)–HAminationReactionswith
Iminoiodinanes 60
2.3.1 CatalyticIntermolecularEnantioselectiveReactions(ChiralityOnlyon
theMetalComplex) 60
2.3.2 CatalyticIntramolecularEnantioselectiveReactions 63
2.3.3 CatalyticIntermolecularDiastereoselectiveReactions(Chiralityonthe
MetalComplexandtheNitrenePrecursor) 66
2.4 CatalyticStereoselectiveC(sp3)–HAminationReactionswith
Azides 67
2.4.1 TransitionMetal-CatalyzedC(sp3)–HAminationReactions 67
2.4.2 EnzymaticC(sp3)–HAminationReactions 68
2.5 CatalyticStereoselectiveC(sp3)–HAminationReactionswith
N-(Sulfonyloxy)carbamates 70
2.6 Conclusion 72
References 72
PartI.B C(sp3)–HActivationasStereodiscriminantStep 77
3 EnantioselectiveIntra-andIntermolecularCouplings 79
QiaoqiaoTengandWei-LiangDuan
3.1 Introduction 79
Contents vii
3.2 EnantioselectiveIntramolecularCouplingsofAliphaticSubstrates 79
3.2.1 C–CCoupling 79
3.2.2 C–XCoupling 89
3.3 EnantioselectiveIntermolecularCouplingsofAliphaticSubstrates 90
3.3.1 PdCatalysis 91
3.3.2 RhCatalysis 102
3.3.3 IrCatalysis 102
3.4 Conclusion 104
References 105
4 Substrate-ControlledTransformation:Diastereoselective
Functionalization 107
Sheng-YiYan,BinLiu,andBing-FengShi
4.1 Introduction 107
4.2 DiastereoselectiveFunctionalizationsofN-Phthaloyl-α-Amino
Acids 108
4.2.1 Diastereoselectiveβ-C(sp3)–HFunctionalizationsof
N-Phthaloyl-α-AminoAcids 108
4.2.1.1 BidentateDirectingGroup 108
4.2.1.2 MonodentateDirectingGroup 114
4.2.2 Diastereoselectiveγ-C(sp3)–HFunctionalizationofα-AminoAcid
Derivatives 114
4.3 DiastereoselectiveC–HActivationControlledbyChiral
Auxiliary 116
4.4 DiastereoselectiveC(sp3)–HFunctionalizationofConformationally
RestrictedCyclicSubstrates 121
4.5 SummaryandConclusions 127
References 128
PartII StereoselectiveSynthesisImplyingActivationof
C(sp2)—HBonds 131
5 PlanarChiralityviaC(sp2)–HActivationInvolvedin
StereodiscriminantStep 133
QingGuandShu-LiYou
5.1 Introduction 133
5.2 DiastereoselectiveSynthesisofPlanarChiralFerrocenes 134
5.3 EnantioselectiveSynthesisofPlanarChiralFerrocenes 134
5.3.1 Pd(II)-CatalyzedDirectC—HBondFunctionalization 134
5.3.2 Pd(0)-CatalyzedDirectC—HBondFunctionalization 140
5.3.3 Ir/Rh-CatalyzedDirectC—HBondFunctionalization 144
5.3.4 Au/Pt-CatalyzedDirectC—HBondFunctionalization 146
5.4 Conclusion 147
References 148
viii Contents
6 AxialChiralityviaC(sp2)–HActivationInvolvedin
StereodiscriminantStep 151
QuentinDherbassy,JoannaWencel-Delord,andFrançoiseColobert
6.1 Introduction 151
6.2 AsymmetricCouplingofTwoArenesbyOxidativeDimerization 152
6.2.1 Copper-CatalyzedReactions 153
6.2.2 Vanadium-CatalyzedReactions 154
6.2.3 Iron-CatalyzedReactions 155
6.2.4 ApplicationintheSynthesisofNaturalProducts 155
6.2.5 Conclusion 156
6.3 StereoselectiveC–HFunctionalizationofProchiralorRacemic
Biaryls 158
6.3.1 AsymmetricC–HAlkylationofNaphthylpyridines 158
6.3.2 DiastereoselectiveC–HFunctionalizationUsingaChiralDirecting
Group 159
6.3.2.1 SulfinylasChiralDirectingGroup 159
6.3.2.2 PhosphatesasChiralDirectingGroup 162
6.3.3 EnantioselectiveC–HFunctionalizationofRacemicBiaryl 163
6.3.4 StereoselectiveC–HFunctionalizationUsingaTransientChiral
DirectingGroup 165
6.3.5 Conclusion 167
6.4 AtroposelectiveCross-CouplingofTwoMoieties 167
6.4.1 Pd-CatalyzedC–HArylationofThiopheneDerivatives 167
6.4.2 Pd-CatalyzedC–HArylationofBiarylSulfoxides 169
6.4.3 Rh-CatalyzedC–HArylationofDiazonaphthoquinones 171
6.4.4 Conclusion 172
6.5 GeneralConclusion 172
References 172
7 CentralChiralityviaAsymmetricC(sp2)–HActivationImplying
DesymmetrizationandKineticResolution 175
SoufyanJerhaoui,FrançoiseColobert,andJoannaWencel-Delord
7.1 SynthesisofC-StereogenicMoleculesviaC(sp2)–H
Functionalization 175
7.1.1 Desymmetrization 175
7.1.2 KineticResolution 182
7.2 SynthesisofP-CentralChiralMoleculesviaC(sp2)–H
Functionalization 183
7.3 SynthesisofChiralOrganosiliconMoleculesviaC(sp2)–H
Functionalization 187
7.4 SynthesisofS-ChiralMoleculesviaC(sp2)–HFunctionalization 189
7.5 Conclusions 190
References 191
Contents ix
8 Non-stereoselectiveC(sp2)–HActivationFollowedbySelective
FunctionalizationofMetallacyclicIntermediate 193
XiaohongChen,XueGong,BoWang,andGuoyongSong
8.1 Introduction 193
8.2 IntramolecularCouplings 194
8.2.1 PalladiumandNickelCatalysis 194
8.2.2 RhodiumCatalysis 196
8.2.3 IridiumCatalysis 200
8.2.4 EnantioselectiveHydroacylation 203
8.3 IntermolecularCouplings 210
8.3.1 RhodiumCatalysis 210
8.3.2 IridiumCatalysis 219
8.3.3 OtherMetalCatalysis 226
8.4 Conclusion 231
Acknowledgments 231
References 231
9 DiastereoselectiveFormationofAlkenesThroughC(sp2)—H
BondActivation 239
ParthasarathyGandeepanandLutzAckermann
9.1 Introduction 239
9.2 C–HActivationwithAlkenes 241
9.2.1 NondirectedC–HAlkenylation 241
9.2.2 DirectedC–HAlkenylation 244
9.3 C–HActivationwithAlkenyl(Pseudo)halides 250
9.4 Hydroarylation 252
9.4.1 HydroarylationofAlkynes 252
9.4.2 HydroarylationofAllenes 257
9.5 Hydroacylation 261
9.5.1 HydroacylationofAlkynes 261
9.5.2 HydroacylationofAllenes 263
9.6 Conclusion 264
References 265
Index 275
xi
Foreword
The ability of metals to cleave and functionalize strong C—H bonds was
discovered in the late nineteenth century. Since then, major conceptual and
methodological breakthrough has been accomplished using transition metal
catalysts,andtheinterestforthisfieldhasexponentiallygrownfromthebegin-
ning of the current century. Nowadays, a wide variety of catalytic methods are
availabletoactivateandfunctionalizedifferenttypesofC—Hbondsinahighly
chemo- and site-selective manner. Whereas these aspects are still progressing,
stereoselectivityhasgainedincreasingmomentumandiscurrentlylyingatthe
forefrontofthefield.
This book, written by specialists of the topic, presents stereoselective C–H
functionalization with a broad coverage, from outer-sphere to inner-sphere
C—Hbondactivationandfromthecontrolofolefingeometrytotheinduction
of point, planar, and axial chirality. Moreover, methods wherein asymmetry is
introduced either during the C–H activation or in a different elementary step
arediscussed.Anotherstrikingfeatureappearingintheenclosedchaptersisthe
diversityofstereogenicelementsthatcannowbeconstructedbyC–Hactivation
methods: single or multiple stereogenic centers, metallocenes with planar
chirality, and biaryl stereogenic axes are all accessible through stereoselective
C–H functionalization. Moreover, the span of enantioselective reactions has
greatly expanded in recent years and now includes almost all facets: desym-
metrization of enantiotopic aryl or alkyl groups; classic, parallel, or dynamic
kinetic resolution; activation of enantiotopic secondary C—H bonds; atrops-
elective cross-coupling; functionalization of pro-atropisomeric systems; etc.
These reactions are increasingly applied to the synthesis of complex molecules
suchasactivepharmaceuticalingredientsandnaturalproducts,andnumerous
examplesareprovidedalongthechapters.
OnecaneasilypredictthatstereoselectiveC—Hbondfunctionalization,which
employs readily available precursors, will become a major tool to make chiral
moleculesforavarietyofapplications,includingattheindustrialscale.Thisbook
willthereforeconstituteaninvaluablesupporttoguidebothacademicandindus-
trialresearchersthroughthesedevelopments.
21December2018 OlivierBaudoin
UniversityofBasel,Switzerland
1
PartI
AsymmetricActivationofC(sp3)—HBonds