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Solvents as reagents in organic synthesis : reactions and applications PDF

544 Pages·2018·35.17 MB·English
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SolventsasReagentsinOrganicSynthesis Solvents as Reagents in Organic Synthesis ReactionsandApplications EditedbyXiao-FengWu Editor AllbookspublishedbyWiley-VCHare carefullyproduced.Nevertheless,authors, Dr.Xiao-FengWu editors,andpublisherdonotwarrantthe Albert-Einstein-Str.29a informationcontainedinthesebooks, 18059Rostock includingthisbook,tobefreeoferrors. Germany Readersareadvisedtokeepinmindthat statements,data,illustrations,procedural Covercredits: detailsorotheritemsmayinadvertentlybe GettyImages/d1sk1ss.deviantart inaccurate. LibraryofCongressCardNo.: appliedfor BritishLibraryCataloguing-in-Publication Data Acataloguerecordforthisbookisavailable fromtheBritishLibrary. Bibliographicinformationpublishedby theDeutscheNationalbibliothek TheDeutscheNationalbibliothek liststhispublicationintheDeutsche Nationalbibliografie;detailedbibliographic dataareavailableontheInternetat <http://dnb.d-nb.de.> ©2018Wiley-VCHVerlagGmbH&Co. KGaA,Boschstr.12,69469Weinheim, Germany Allrightsreserved(includingthoseoftrans- lationintootherlanguages).Nopartofthis bookmaybereproducedinanyform–by photoprinting,microfilm,oranyother means–nortransmittedortranslatedinto amachinelanguagewithoutwrittenpermis- sionfromthepublishers.Registerednames, trademarks,etc.usedinthisbook,even whennotspecificallymarkedassuch,are nottobeconsideredunprotectedbylaw. PrintISBN:978-3-527-34196-2 ePDFISBN:978-3-527-80561-7 ePubISBN:978-3-527-80563-1 MobiISBN:978-3-527-80564-8 oBookISBN:978-3-527-80562-4 CoverDesign Adam-Design,Weinheim, Germany Typesetting SPiGlobal,Chennai,India PrintingandBinding Printedonacid-freepaper 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

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