Table Of ContentChiral Ferrocenes in
Asymmetric Catalysis
Edited by
Li-Xin Dai and Xue-Long Hou
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Chiral Ferrocenes in Asymmetric Catalysis
Synthesis and Applications
Edited by
Li-Xin Dai and Xue-Long Hou
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ISBN:978-3-527-32280-0
V
Contents
List of Contributors XV
1 Introduction 1
Li-XinDaiandXue-LongHou
1.1 Foreword 1
1.2 PlanarChiralityofFerrocenylLigands 4
1.3 DerivatizationoftheFerroceneScaffold 6
1.4 Stability,RigidityandBulkinessoftheFerroceneScaffold 9
1.5 Outlook 10
References 11
2 StereoselectiveSynthesisofPlanarChiralFerrocenes 15
Wei-PingDeng,VictorSnieckus,andCostaMetallinos
2.1 Introduction 15
2.2 DiastereoselectiveDirectedortho-MetalationofFerroceneswith
ChiralAuxiliaries 19
2.2.1 Ugi'sAmineandOtherChirala-Substituted
Ferrocenylmethylamines 20
2.2.2 ChiralSulfoxides 23
2.2.3 ChiralAcetals 26
2.2.4 ChiralOxazolines 29
2.2.5 OtherChiralAuxiliaries 31
2.3 EnantioselectiveDirectedortho-MetalationofFerroceneswith
ChiralBases 36
2.4 EnzymaticandNonenzymaticKineticResolutions 40
2.4.1 EnzymaticKineticResolutions 40
2.4.2 NonenzymaticKineticResolutions 41
2.5 SummaryandPerspectives 42
2.6 SelectedExperimentalProcedures 44
ChiralFerrocenesinAsymmetricCatalysis.EditedbyLi-XinDaiandXue-LongHou
Copyright(cid:1)2010WILEY-VCHVerlagGmbH&Co.KGaA,Weinheim
ISBN:978-3-527-32280-0
VI Contents
2.6.1 Synthesisof(R,Sp)-N,N-dimethyl-1-(2-diphenylphosphino-ferrocenyl)
ethylamine(PPFA) 44
2.6.1.1 SynthesisofRacemica-Ferrocenylethyldimethylamine 44
2.6.1.2 Resolutionofa-Ferrocenylethyldimethylamine 45
2.6.1.3 Synthesisof(R,Sp)-N,N-dimethyl-1-(2-diphenylphosphinoferrocenyl)
ethylamine(PPFA) 45
2.6.2 Synthesisof(R,Rp)-1-(tert-butylsulfinyl)-2-(diphenylphosphino)-
ferrocene 45
2.6.2.1 Synthesisof(R)-tert-butylsulfinylferrocene(R) 45
2.6.2.2 Synthesisof(R,Rp)-1-(tert-Butylsulfinyl)-2-(diphenylphosphino)
ferrocene 46
2.6.3 SynthesisofFcPHOX 46
2.6.3.1 Synthesisof(S)-2-ferrocenyl-4-(1-methylethyl)oxazoline 46
2.6.3.2 Synthesisof(S,Sp)-2-[2-(diphenylphosphino)ferrocenyl]-4-
(1-methylethyl)oxazoline 47
2.6.4 Synthesisof(Sp)-N,N-diisopropyl-2-(diphenylphosphino)
ferrocenecarboxamide 48
2.6.4.1 (Sp)-N,N-diisopropyl-2-(diphenylphosphino)
ferrocenecarboxamide 48
References 49
3 MonodentateChiralFerrocenylLigands 55
Ji-BaoXia,TimothyF.Jamison,andShu-LiYou
3.1 Introduction 55
3.2 Nickel-CatalyzedAsymmetricReductiveCouplingReactions 55
3.2.1 SynthesisofP-Chiral,MonodentateFerrocenylPhosphines 56
3.2.2 Nickel-CatalyzedAsymmetricReductiveCouplingofAlkynes
andAldehydes 56
3.2.3 Nickel-CatalyzedAsymmetricReductiveCouplingofAlkynes
andKetones 60
3.2.4 Nickel-CatalyzedAsymmetricThree-ComponentCouplingof
Alkynes,Imines,andOrganoboronReagents 61
3.3 Copper(I)-CatalyzedAsymmetricAllylicAlkylationReactions 62
3.4 AsymmetricSuzuki–MiyauraReactions 64
3.5 AdditionofOrganoaluminumtoAldehydesandEnones 65
3.6 AsymmetricNucleophilicCatalysis 66
3.7 ConclusionandPerspectives 70
References 70
4 Bidentate1,2-FerrocenylDiphosphineLigands 73
Hans-UlrichBlaserandMatthiasLotz
4.1 Introduction 73
4.2 TypeABothPR2GroupsAttachedtotheCpRing 74
4.3 TypeBOnePR2GroupAttachedtotheCpRing,onePR2Group
Attachedtothea-PositionoftheSideChain 75
Contents VII
4.3.1 Josiphos 76
4.3.2 ImmobilizedJosiphos 80
4.3.3 JosiphosAnalogs 82
4.4 TypeCOnePR2GroupAttachedtotheCpRing,onePR2
GroupAttachedtotheb-PositionoftheSideChain 83
4.4.1 BoPhozandAnalogs 83
4.5 TypeD,OnePR2GroupAttachedtotheCpRing,OnePR2
GroupAttachedtoOtherPositionsoftheSideChain 85
4.5.1 Taniaphos 86
4.6 TypeE,BothPR2GroupsAttachedtoSideChains 87
4.6.1 Walphos 88
4.6.2 TRAP 90
References 91
5 1,2-P,N-BidentateFerrocenylLigands 97
YongGuiZhouandXueLongHou
5.1 Introduction 97
5.2 AsymmetricHydrogenationandAsymmetricTransfer
Hydrogenation 97
5.2.1 AsymmetricHydrogenation 97
5.2.1.1 AsymmetricHydrogenationofAlkenes 98
5.2.1.2 AsymmetricHydrogenationofKetones 101
5.2.1.3 AsymmetricHydrogenationofHeteroaromaticCompounds 103
5.2.1.4 AsymmetricHydrogenationofImines 104
5.2.2 AsymmetricTransferHydrogenation 106
5.2.3 AsymmetricHydrosilylationReaction 109
5.2.3.1 Palladium-CatalyzedAsymmetricHydrosilylation
ofC¼CBond 110
5.2.3.2 AsymmetricHydrosilylationofaC¼OBond 112
5.2.3.3 AsymmetricHydrosilylationoftheC¼NBond 117
5.2.4 AsymmetricHydroboration 118
5.3 FormationofaC–CBond 121
5.3.1 Pd-CatalyzedAsymmetricAllylicSubstitutionReaction 121
5.3.2 AsymmetricHeckReactionandCross-CouplingReactions 126
5.3.3 AdditionofOrganometallicReagentstoaC¼XBond 129
5.4 CycloadditionReactions 132
5.4.1 [3þ2]CycloadditionReactions 132
5.4.2 AsymmetricCyclopropanationReactions 136
5.4.3 AsymmetricDiels-AlderReactions 136
5.5 MiscellaneousReactions 137
5.6 ConclusionandPerspectives 140
5.7 Experimental:SelectedProcedures 140
5.7.1 UgisAmineSynthesis 140
5.7.1.1 Synthesisofa-Ferrocenylethyldimethylamine(2) 141
5.7.1.2 Resolutionof2 141
VIII Contents
5.7.1.3 Synthesisof(S)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)
ferrocenyl]ethylamine 141
5.7.2 (S,Sp)-2-[(S)-2-(diphenylphosphino)ferrocenyl]-4-(1-methylethyl)
oxazoline 142
5.7.2.1 Synthesisof(2S)-N-(1-hydroxy-3-methylbutyl)ferrocenamide 142
5.7.2.2 SynthesisofFerrocenyloxazoline 142
5.7.2.3 Synthesisof(S,Sp)-2-[(S)-2-(diphenylphosphino)ferrocenyl]-4-
(1-methylethyl)oxazoline 143
References 144
6 N,O-BidentateFerrocenylLigands 149
AnneNijs,OlgaGarcíaMancheño,andCarstenBolm
6.1 Introduction 149
6.2 AdditionofOrganozincReagentstoAldehydes 149
6.2.1 AdditionofDialkylzinc 150
6.2.1.1 WithFerrocenylAminoAlcohols 150
6.2.1.2 WithFerrocenylOxazolinylAlcohols 158
6.2.1.3 WithAzaferrocenes 160
6.2.2 AdditionofArylzinc 161
6.2.3 AdditionofPhenylacetylene 165
6.3 AdditiontoAldehydeswithBoronReagents 165
6.3.1 ArylTransferswithBoronicEsters 165
6.3.2 ArylTransferwithTriphenylborane[Ph B] 166
3
6.3.3 BoronicAcidsasArylSource 167
6.3.4 AlkenylboronicAcidsinAlkenylTransferReactions 168
6.4 OtherTransformations:AsymmetricEpoxidation 168
6.5 ConclusionandPerspectives 169
6.6 Experimental:SelectedProcedures 170
6.6.1 AdditionofDiethylzinctoBenzaldehydewithFerrocene13 170
6.6.2 PhenylacetyleneAdditiontoAldehydeswithFerrocene24 170
6.6.3 PhenylTransfer(ZnEt þZnPh )toAldehydeswithFerrocene13 171
2 2
6.6.4 PhenylTransfertoAldehydeswithTriphenylboraneona
GramScale 171
6.6.5 ArylTransfertoAldehydeswithBoronicAcidsonaMultigram
Scale 171
References 173
7 Symmetrical1,10-BidentateFerrocenylLigands 175
WanbinZhangandDelongLiu
7.1 Introduction 175
7.2 Symmetrical1,10-DisubstitutedFerrocenylLigands 177
7.2.1 P-CenteredChiralDiphosphineLigands 177
7.2.2 C-CenteredChiralDiphosphineLigands 180
7.2.3 ChiralNitrogen-ContainingLigands 188
7.3 Symmetrical1,1,2,20-TetrasubstitutedFerrocenylLigands 193
Contents IX
7.3.1 TetrasubstitutedFerrocenylDiphosphineLigandswith
Multi-Chiralities 193
7.3.2 TetrasubstitutedFerrocenylLigandswithOnlyPlanarChirality 198
7.3.3 OtherTetrasubstitutedFerrocenylLigands 201
7.4 AnalogsofFerrocenes:Symmetrical1,10-Bidentate
RuthenocenylLigands 203
7.5 ConclusionandPerspectives 208
7.6 Experimental:SelectedProcedures 208
7.6.1 TypicalProcedureforthePreparationof
FerrocenyldiphosphinesL-2 208
7.6.2 TypicalProcedureforthePreparationofthe(R,R)-ferrocenyl
Diol14 208
7.6.3 TypicalProcedureforthePreparationof(aR,a0R)-2,20-
Bis(a-N,N-dimethylaminopropyl)-(S,S)-1,10-
bis(diphenylphosphino)ferroceneL-17c 209
7.6.4 TypicalProcedureforthePreparationofC -Symmetric
2
1,10,2,20-tetrasubstitutedFerroceneDerivativesL-18 209
7.6.5 TypicalProcedureforthePreparationoftheFerrocene-Based
EsterAmide59 209
7.6.6 TypicalProcedureforthePreparationof((cid:1))-(S)-(S)-1,10-
Bis(diphenylphosphino)-2,20-bis-(methoxycarbonyl)ferroceneL-21 210
7.6.7 TypicalProcedureforthePreparationof1,10-Bis[(S)-4-
isopropyloxazolin-2-yl]-ruthenocene82 210
References 211
8 Unsymmetrical1,10-BidentateFerrocenylLigands 215
Shu-LiYou
8.1 Introduction 215
8.2 Palladium-CatalyzedAsymmetricAllylicSubstitutionReaction 215
8.2.1 AModelReactionofSymmetrical1,3-Disubstituted2-Propenyl
Acetates 216
8.2.2 SubstrateVariantsofPalladium-CatalyzedAsymmetric
AllylicSubstitutionReaction 221
8.2.3 RegioselectiveControlforUnsymmetricalAllylicAcetates 224
8.2.4 ApplicationsofPalladium-CatalyzedAsymmetricAllylic
SubstitutionReaction 228
8.3 GoldorSilver-CatalyzedAsymmetricAldolReactions 229
8.3.1 Gold-CatalyzedAsymmetricAldolReactions 229
8.3.2 Silver-CatalyzedAsymmetricAldolReactions 232
8.3.3 ApplicationsofGoldorSilver-CatalyzedAsymmetric
AldolReactions 232
8.4 AsymmetricHydrogenation 234
8.4.1 Rh-CatalyzedHydrosilylation 234
8.4.2 Rh,Ir,Ru-CatalyzedHydrogenation 235
8.4.3 Rh-CatalyzedHydroboration 238
X Contents
8.5 AsymmetricCross-CouplingReaction 239
8.5.1 Nickel-CatalyzedKumadaCouplingReaction 239
8.5.2 Palladium-CatalyzedCross-CouplingReaction 240
8.5.3 Palladium-CatalyzedSuzuki–MiyauraReactionanda-Arylation
ofAmides 241
8.6 AsymmetricHeckReaction 242
8.6.1 IntramolecularHeckReaction 242
8.6.2 IntermolecularHeckReaction 243
8.7 Miscellaneous 244
8.7.1 AdditionofZincReagenttoAldehydes 244
8.7.2 ConjugateAddition 247
8.7.3 Rh-CatalyzedRingOpeningReactionof
Oxabenzonorbornadiene 247
8.7.4 AsymmetricCyclopropanationofAlkeneswithDiazoEsters 248
8.7.5 AsymmetricPalladium-CatalyzedHydroesterificationofStyrene 249
8.8 ConclusionandPerspectives 250
8.9 Experimental:SelectedProcedures 250
8.9.1 SynthesisofCompound(S,Sp)-L4dfrom(S)-5a 250
8.9.2 SynthesisofCompound(S,Rphos,R)-L8dand(S,Sphos,R)-L8d
from(S)-5d 251
References 253
9 Sulfur-andSelenium-ContainingFerrocenylLigands 257
JuanC.Carretero,JavierAdrio,andMartaRodríguezRivero
9.1 Introduction 257
9.2 AsymmetricAllylicSubstitution 258
9.2.1 Palladium-CatalyzedAllylicSubstitution 258
9.2.1.1 BidentateN,S-ferroceneLigands 259
9.2.1.2 BidentateP,S-ferroceneLigands 260
9.2.2 Copper-CatalyzedAllylicSubstitution 265
9.3 OtherAsymmetricPalladium-CatalyzedReactions 266
9.3.1 AsymmetricHeckReactions 266
9.3.2 DesymmetrizationofHeterobicyclicAlkenes 267
9.4 Gold-CatalyzedReactions 268
9.5 AsymmetricReductions 269
9.6 Asymmetric1,2-and1,4-NucleophilicAddition 270
9.6.1 Asymmetric1,2AdditiontoAldehydesandImines 270
9.6.2 Asymmetric1,4-ConjugateAddition 272
9.7 AsymmetricCycloadditionReactions 272
9.7.1 [4þ2]Cycloadditions 272
9.7.2 [3þ2]Cycloadditions 274
9.8 AsymmetricNucleophilicCatalysis 276
9.9 ConclusionandPerspectives 277
9.10 Experimental:SelectedProcedures 278
9.10.1 Palladium-CatalyzedAllylicAlkylationReactionwithLigand3a 278
