Solvents as reagents in organic synthesis : reactions and applications

544 Pages·2018·35.17 MB·English

by  Wu

SolventsasReagentsinOrganicSynthesis
Solvents as Reagents in Organic Synthesis
ReactionsandApplications
EditedbyXiao-FengWu
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v
Contents
ListofContributors xiii
1 TheApplicationsofWaterasReagentsinOrganicSynthesis 1
ZhengkaiChenandHongjunRen
1.1 Introduction 1
1.2 IncorporationofHydrogenAtomfromtheWater 2
1.2.1 1,2,3-Triazoles 4
1.3 IncorporationofOxygenAtomfromtheWater 7
1.4 IncorporationofHydroxylGroupfromWater 31
1.5 TracelessPromotionoftheReactionsbyWater 39
1.6 Conclusions 44
References 44
2 TheApplicationsofTolueneandXylenes 49
KrishnaNandSingh,NarendraR.Chaubey,andNeetuSingh
2.1 ApplicationofTolueneandXylenesasReagents 50
2.2 OxidationofMethylGroupintoCommonFunctionalities 50
2.3 ApplicationofMethylGroupasAcylBuildingBlock 51
2.3.1 SynthesisofCarbonylCompounds 51
2.3.2 SynthesisofAmides 53
2.3.3 SynthesisofN-AroylSulfoximines 54
2.3.4 SynthesisofEsters 55
2.3.5 SynthesisofThioesters 56
2.4 ApplicationasAlkylBuildingBlock 60
2.4.1 SynthesisofNitriles 60
2.4.2 Synthesisof2-PhenylAceticAcidDerivatives 61
2.4.3 AlkylationofSulfonamides 62
2.4.4 AlkylationofThiophenols 63
2.4.5 SynthesisofTrifluoromethylSulfides 64
2.4.6 SynthesisofBenzylEsters 64
2.4.7 SynthesisofPhosphateEsters 66
2.4.8 SynthesisofCarbamates,Thioamides,andEsters 66
2.4.9 Synthesisof3-BenzylCoumarinDerivatives 66
2.4.10 DecarboxylativeBenzylationofCinnamicAcids 68
2.4.11 SynthesisofFunctionalizedOxindoles 68
vi Contents
2.4.12 SynthesisofDihydroquinolinones 69
2.4.13 BenzylationofEnones 69
2.4.14 Couplingwith1,3-DicarbonylCompounds 70
2.4.15 BenzylationofPyridine-N-Oxide 70
2.4.16 SynthesisofDihydrofurans 70
2.4.17 SynthesisofQuinolineDerivatives 71
2.4.18 ReactionwithEthylDiazoacetate 72
2.4.19 SynthesisofBenzo[b]phospholeOxides 72
2.4.20 Synthesisofβ-Aromaticα-AminoAcidDerivatives 73
2.4.21 HalogenationReactions 73
2.4.22 N-BenzylationofIsoquinolines 75
2.5 ApplicationasEstersBuildingBlock 76
2.6 ApplicationasAlcoholsBuildingBlock 77
References 77
3 TheApplicationsof1,4-Dioxane,THF,andEthersasVersatile
BuildingBlocksinOrganicSynthesis 81
PingLiu,GuanghuiZhang,andPeipeiSun
3.1 Introduction 81
3.2 CleavageofC(sp3)–HofEthers 82
3.2.1 Cross-DehydrogenativeCouplingReactionsofEthers 82
3.2.1.1 C–CBondFormation 83
3.2.1.2 C–NBondFormation 91
3.2.1.3 C–OBondFormation 93
3.2.2 TheFormationofC–SBond 97
3.2.3 AdditionofEtherstoC=CandC≡CBonds 98
3.2.4 DecarboxylativeAlkenylationorAlkylationReactions 104
3.2.5 RadicalAlkenylationandAlkynylationofEthers 106
3.2.6 Radicalα-C–HHydroxyalkylationandAminoalkylationof
Ethers 107
3.2.7 IntermolecularCarbenoidInsertiontoα-C–HBondofEthers 109
3.2.8 C(sp3)–HArylationwithArylmetalorArylboronReagents 109
3.3 CleavageofC–OofEthers 112
3.4 CleavageofC–CBondsofEthers 117
3.5 Conclusion 118
References 118
4 TheApplicationofDichloromethaneandChloroformas
ReagentsinOrganicSynthesis 125
AnisTliliandJohannesSchranck
4.1 TheApplicationofDichloromethaneandChloroformasReagentsin
OrganicSynthesis 125
4.1.1 Dichloromethane 125
4.1.1.1 ReactionsofDichloromethanewithPosttransitionMetals 126
4.1.1.2 ReactionsofDichloromethanewithTransitionMetals 127
4.1.1.3 ReactionsofDichloromethanewithPhosphines 135
Contents vii
4.1.1.4 ReactionsofDichloromethanewithAminesandPhosphines 136
4.1.1.5 ReactionsofDichloromethanewithAmines 136
4.1.1.6 ReactionsofDichloromethanewithAminesandNucleophilicCarbon
Derivatives 139
4.1.1.7 ReactionofDichloromethanewithNucleophilicSulfur 141
4.1.2 Chloroform 142
4.1.2.1 ReactionofChloroformwithHydrogenFluoride 142
4.1.2.2 ReactionsofChloroformwithPost-TransitionMetals 142
4.1.2.3 ReactionsofChloroformwithTransitionMetals 143
4.1.2.4 FormationandUseofDichlorocarbene 146
References 154
5 TheApplicationsofAcetoneandEthylAcetate 161
Jie-PingWan
5.1 Acetone 161
5.1.1 AldolReaction 161
5.1.2 Claisen–SchmidtReaction 167
5.1.3 MannichReaction 170
5.1.4 Miscellaneous 175
5.2 EthylAcetate 182
5.2.1 Transesterification 183
5.2.2 Amidation 187
5.2.3 Miscellaneous 190
References 192
6 N,N-DimethylformamideandN,N-Dimethylacetamideas
Carbon,Hydrogen,Nitrogen,and/orOxygenSources 199
JeanLeBrasandJacquesMuzart
6.1 Introduction 199
6.2 Amination 200
6.2.1 Benzylicand(Hetero)arylHalides 200
6.2.2 BenzylandAllylAcetates 205
6.2.3 KetonesandAldehydes 206
6.2.4 Azoles 207
6.2.5 Others 208
6.3 AmidationandThioamidation 209
6.3.1 UsingtheDMDimethylamineMoiety 209
6.3.1.1 ArylandAlkenylHalidesorTriflates 209
6.3.1.2 AcylHalides 210
6.3.1.3 CarboxylicAcids,α-Ketoacids,Esters,Peresters,andAnhydrides 211
6.3.1.4 PrimaryAlcoholsandAldehydes 216
6.3.1.5 MethylKetones 217
6.3.1.6 Nitriles 218
6.3.1.7 Dibenzyldisulfanes 219
6.3.2 UsingtheDMDimethylcarbamoylMoiety 219
6.3.2.1 ArylHalides 219
6.3.2.2 Ketones 221
viii Contents
6.3.2.3 β-DicarbonylCompounds 221
6.3.2.4 Phenols 221
6.3.2.5 Thiophenols 223
6.3.2.6 Alkenes 223
6.3.2.7 Alkynes 223
6.3.2.8 Amines 224
6.3.2.9 Amides 225
6.3.2.10 Nitriles 225
6.3.2.11 Isonitriles 226
6.3.2.12 Benzothiazoles 226
6.3.2.13 SelenidesandSulfides 226
6.3.2.14 Aryl-TetheredActivatedAlkenes 227
6.3.3 UsingtheDMFormyl/AcetylMoiety 227
6.3.4 UsingtheDMFDimethylamino-CarbonMoiety 231
6.3.5 UsingCH,CHCONMe ,CH CONMe ,orH(Me)CONMeCH Moiety
2 2 2 2
ofDM 233
6.3.5.1 Alcohols 233
6.3.5.2 AldehydesandKetones 234
6.3.5.3 CarboxylicAcidsandα-Ketoacids 235
6.3.5.4 Amines 235
6.3.5.5 ImidesandAmides 236
6.3.5.6 Alkenes 237
6.3.5.7 Sulfides 237
6.3.5.8 (Hetero)arenes 238
6.3.5.9 DominoReactions 240
6.4 Amidination 241
6.4.1 Sulfonamides 241
6.4.2 Enamines 242
6.5 FormylationandRelatedDominoReactions 242
6.5.1 Vilsmeier-MediatedFormylations 243
6.5.1.1 (Hetero)arenes 243
6.5.1.2 Alkenes 245
6.5.1.3 O-SilylatedEthers 246
6.5.1.4 AlcoholsandPhenols 246
6.5.1.5 Enamines 247
6.5.1.6 ActivatedMethylGroups 247
6.5.2 Vilsmeier-MediatedDominoReactions 247
6.5.2.1 FormylationandCyclization 247
6.5.2.2 Haloformylation 249
6.5.2.3 HaloformylationandCyclization 250
6.5.2.4 RingOpening,Haloformylation,andCyclization 252
6.5.2.5 Diformylation 253
6.5.2.6 IntramolecularFormylation-IntermediateTrapping 254
6.5.3 UsingOrganolithiensorOrganomagnesiens 256
6.5.4 Hydroformylation 258
6.5.5 Formoxylation 259
6.6 Carbonylation 260
Contents ix
6.6.1 CarbonylfromDMF 260
6.6.2 CarbonfromDMDimethylamineMoiety 262
6.7 Cyanation 264
6.7.1 CarbonfromDMFCarbonyl 264
6.7.1.1 VilsmeierProcedure 264
6.7.1.2 n-BuLi(orMg)/I /NH Procedure 265
2 3
6.7.2 CarbonfromDMDimethyl 266
6.7.2.1 Pd/CuProcedure 266
6.7.2.2 CuProcedure 267
6.7.3 CarbonandNitrogenfromDMDimethyl 269
6.7.3.1 PdProcedure 269
6.7.3.2 CuProcedure 270
6.8 InsertionReactions 271
6.8.1 Alkenes 271
6.8.2 Alkynes 272
6.8.3 Arynes 274
6.8.4 Imines 276
6.8.5 Carbenes 276
6.8.6 Nitriles 278
6.9 MiscellaneousReactions 278
6.9.1 Cycloaddition 278
6.9.2 Methylenation 278
6.9.2.1 OfBenzylicCarbons 278
6.9.2.2 OfAromaticCarbons 280
6.9.2.3 OfEnolicCarbons 282
6.9.3 Methylidynation 283
6.9.4 Acetylation 285
6.9.5 EtherFormation 285
6.9.6 AnhydrideFormation 286
6.9.7 Substitution 286
6.9.8 HydrogenDelivery 289
6.9.9 AcetalizationofDMF 294
6.9.10 ThionationofDM 294
6.9.11 HydrodeoxygenationofDMF 294
Acknowledgments 295
References 296
7 TheApplicationsofDMSO 315
Jia-ChenXiang,Qing-HeGao,andAn-XinWu
7.1 ABriefIntroductionofDMSO 315
7.2 NameReactions 316
7.2.1 SwernOxidation 316
7.2.2 Parikh–DoeringOxidation 316
7.2.3 Pfitzner–MoffattOxidation 317
7.2.4 KornblumOxidation 317
7.3 AsReactionReagents 318
7.3.1 Providing–OH(HydroxylationReagent) 318
x Contents
7.3.2 Providing–CO(CarbonylationReagent) 320
7.3.3 Providing–SO Me(SulfonylationReagent) 321
2
7.3.4 DMSOServesasaSourceofSulfur 324
7.3.4.1 Providing–MeSMeGroup 324
7.3.4.2 Providing–SMeGroup 326
7.3.4.3 Providing–SOMeGroup 331
7.3.5 AsOne-CarbonSynthon 332
7.3.5.1 MethylationReagent 332
7.3.5.2 FormylationReagent 332
7.3.5.3 CyanationReagent 335
7.3.5.4 One-CarbonUnittoParticipateintheRingorBridgeFormation 336
7.3.6 DimsylAnionActivationReagent 339
7.4 AsMultifunctionalCatalyst/ReagentinSelf-SortingReaction
System 342
7.5 SummaryandPerspectives 349
Acknowledgments 349
References 349
8 AcetonitrileasReagentsinOrganicSynthesis:Reactionsand
Applications 355
Shun-YiWang,Xue-QiangChu,YiFang,andShun-JunJi
8.1 Introduction 355
8.2 Transition-Metal-CatalyzedCross-CouplingofAcetonitrileand
Nitriles 355
8.3 Free-Radical-InitiatedC–HFunctionalizationofAcetonitrileand
Nitriles 366
8.4 SummaryandOutlook 374
Acknowledgments 374
References 374
9 TheApplicationsofNitromethaneasReagentandSolventin
OrganicSynthesis 377
XinxinQi,Jin-BaoPeng,andXiao-FengWu
9.1 Introduction 377
9.2 ReactionswithAldehydes 377
9.3 ReactionswithImines 385
9.4 ReactionswithKetones 387
9.5 MichaelReaction 388
9.6 OtherReactions 391
References 395
10 AlcoholasaReagentinHomogeneousCatalysis 403
FengHan,WeiSun,ChunguXia,andChaoLiu
10.1 Introduction 403
10.2 AlcoholasO-nucleophile 403
10.2.1 EsterificationReaction 403