Reactive Intermediates: MS Investigations in Solution PDF
Preview Reactive Intermediates: MS Investigations in Solution
Reactive Intermediates Edited by Leonardo S. Santos Related Titles Downard, K.(ed.) Mass Spectrometry of Protein Interactions 2007 ISBN:978-0-471-79373-1 Platz,M. S., Moss,R. A., Jones,M. (eds.) Reviews of Reactive Intermediate Chemistry 2007 ISBN:978-0-471-73166-5 Hillenkamp, F.,Peter-Katalinic, J. (eds.) MALDI MS APracticalGuidetoInstrumentation,MethodsandApplications 2007 ISBN:978-3-527-31440-9 Niemantsverdriet, J. W. Spectroscopy in Catalysis AnIntroduction Third,CompletelyRevisedandEnlargedEdition 2007 ISBN:978-3-527-31651-9 de Hoffmann, E., Stroobant,V. Mass Spectrometry PrinciplesandApplications ThirdEdition 2007 ISBN:978-0-471-48565-0 Reactive Intermediates MS Investigations in Solution Edited by Leonardo S. Santos TheEditor AllbookspublishedbyWiley-VCHarecarefully produced.Nevertheless,authors,editors,and Dr.LeonardoS.Santos publisherdonotwarranttheinformationcontained TalcaUniversity inthesebooks,includingthisbook,tobefreeof ChemistryInstituteofNaturalResources errors.Readersareadvisedtokeepinmindthat AvenidaLircays/n statements,data,illustrations,proceduraldetailsor Talca otheritemsmayinadvertentlybeinaccurate. Chile LibraryofCongressCardNo.: appliedfor BritishLibraryCataloguing-in-PublicationData Acataloguerecordforthisbookisavailablefromthe BritishLibrary. Bibliographicinformationpublishedby theDeutscheNationalbibliothek DieDeutscheNationalbibliothekliststhis publicationintheDeutscheNationalbibliografie; detailedbibliographicdataareavailableonthe Internetathttp://dnb.d-nb.de. #2010WILEY-VCHVerlagGmbH&Co.KGaA, Weinheim Allrightsreserved(includingthoseoftranslationinto otherlanguages).Nopartofthisbookmaybe reproducedinanyform–byphotoprinting, microfilm,oranyothermeans–nortransmittedor translatedintoamachinelanguagewithoutwritten permissionfromthepublishers.Registerednames, trademarks,etc.usedinthisbook,evenwhennot specificallymarkedassuch,arenottobeconsidered unprotectedbylaw. PrintedintheFederalRepublicofGermany Printedonacid-freepaper ISBN:978-3-527-32351-7 Cover Grafik-DesignSchulz,Fußgönnheim To Gisa, Guilherme and Larissa whose patience and love enable them to hold out the hours of homework and the moments of my absence VII Contents Foreword XIII Preface XXI List of Contributors XXIII 1 ABriefOverviewoftheMechanismsInvolvedinElectrospray MassSpectrometry 1 PaulKebarleandUdoH.Verkerk 1.1 Introduction 1 1.1.1 OriginsofElectrosprayMassSpectrometry 1 1.1.2 AimsofthisChapter 2 1.2 ProductionofGas-PhaseIonsbyElectrosprayandElectrospray IonizationMassSpectrometry 3 1.2.1 Overview 3 1.2.2 ProductionofChargedDropletsattheCapillaryTip 5 1.2.3 ElectrosprayasanElectrolyticCell 7 1.2.4 RequiredElectricalPotentialsforES.ElectricalGasDischarges 8 1.2.5 Current,ChargeandRadiusofDropletsProducedatthe CapillaryTip 10 1.2.6 SolventEvaporationfromChargedDropletsCausesCoulomb FissionsofDroplets 10 1.2.7 EvaporationofDropletsLeadingtoCoulombFissionsProducing ProgenyDropletsthatUltimatelyLeadtoIonsintheGas-Phase; EffectsoftheConcurrentLargeConcentrationIncrease 11 1.2.8 MechanismfortheFormationofGas-PhaseIonsfromVerySmall andHighlyChargedDroplets.TheIonEvaporationModel(IEM) 15 1.2.9 ObservedRelativeIonIntensityofSmallAnalytes.Dependence ontheNatureoftheAnalyte,itsConcentrationandPresenceof OtherElectrolytesintheSolution.HighSensitivitiesof Surface-ActiveAnalytes 17 1.2.10 LargeAnalyteIonssuchasDendrimersandProteinsareMost ProbablyProducedbytheChargedResidueModel(CRM) 22 ReactiveIntermediates:MSInvestigationsinSolution.EditedbyLeonardoS.Santos. Copyright(cid:1)2010WILEY-VCHVerlagGmbH&Co.KGaA,Weinheim ISBN:978-3-527-32351-7 VIII Contents 1.2.11 NanosprayandInsightsintoFundamentalsofElectroand Nanospray 26 1.2.12 ConsequencesoftheIncreaseinConcentrationCausedby ExtensiveEvaporationofSolventinESIProcess.Promotionof BimolecularReactionsInvolvingAnalyteIons 28 1.2.12.1 Positive-NegativeIon-PairingReactionsInvolvingImpurities þ suchasNa 28 1.2.12.2 DeterminationofEquilibriumConstantsinSolutionviaESI-MS 29 References 31 2 HistoricalPerspectivesintheStudyofIonChemistrybyMass Spectrometry:FromtheGasPhasetoSolution 37 HaoChen 2.1 ABriefHistoryandRecentAdvancesinMassSpectrometry 38 2.1.1 EarlyDevelopments 38 2.1.2 RecentAdvances 40 2.2 OverviewoftheStudyofIon/MoleculeReactionsintheGas PhasebyMassSpectrometry 41 2.2.1 BriefHistory 41 2.2.2 BasicTypesofIon/MoleculeReactions 42 2.2.3 RelationshiptoReactionAnalogiesinSolution 43 2.2.3.1 MechanismElucidationofClassicalOrganicReactions 43 2.2.3.2 MechanismElucidationofOrganometallicReactions 44 2.2.3.3 CatalystScreening 49 2.2.3.4 SynthesisofElusiveIonicSpecies 49 2.2.3.5 ProbingReactivityofMicrosolvatedClusterIons 50 2.2.4 ExperimentalMethodsfortheStudyofIon/MoleculeReactions 50 2.2.4.1 Low-PressureIon/MoleculeReactions 50 2.2.4.2 High-PressureIon/MoleculeReactions 51 2.3 FuturePerspectives 52 References 53 3 OrganicReactionStudiesbyESI-MS 63 FabianeM.NachtigallandMarcosN.Eberlin 3.1 Introduction 63 3.2 ReactionMechanisms 65 3.2.1 Morita-Baylis-HillmanReaction 65 3.2.2 Morita-Baylis-HillmanReactionCo-catalyzedbyIonicLiquids 67 3.2.3 a-MethylenationofKetoesters 71 3.2.4 UnexpectedSynthesisofConformationallyRestrictedAnalogs ofg-AminoButyricAcid(GABA)viaaRingContractionReaction 73 3.2.5 TheHeckReaction 75 3.2.6 SuzukiReaction 81 3.2.7 StilleReaction 81 3.2.8 Three-ComponentPd(0)-CatalyzedTandemDouble Addition-CyclizationReaction 83 Contents IX 3.2.9 AlkynilationofTelluridesMediatedbyPd(II) 84 3.2.10 TeCl AdditiontoPropargylAlcohols 88 4 3.2.11 S 2Reactions 89 N 3.2.12 AllylicSubstitutionReaction 91 3.2.13 HeterogeneousFentonReaction 93 3.2.14 MimickingtheAtmosphericOxidationofIsoprene 93 3.2.15 AdvancedOxidationProcessesofEnvironmentalImportance 95 3.2.16 TrögersBases 96 3.2.17 TheThree-ComponentBiginelliReaction 98 3.2.18 ModelingtheRibonucleaseMechanism 103 3.2.19 OxidativeCleavageofTerminalC¼Cbonds 105 3.3 GeneralRemarks 108 References 108 4 StudiesofReactionMechanismIntermediatesbyESI-MS 113 RongQian,JingZhou,ShengjunYao,HaoyangWang,andYinlongGuo 4.1 Introduction 113 4.2 StudiesontheIntermediatesandMechanismsofPd-Catalyzed Reactions 113 4.3 StudiesonSomeReactiveIntermediatesandMechanisms ofRadicalReactions 115 4.4 StudiesontheIntermediatesandMechanismofOrganocatalysis Reactions 121 4.5 StudiesontheIntermediatesandMechanismofTransition Metal-CatalyzedPolymerizationReactions 123 References 129 5 On-lineMonitoringReactionsbyElectrosprayIonization MassSpectrometry 133 LeonardoS.Santos 5.1 Introduction 133 5.2 PreservationoftheChargeintheTransitofIonsfromSolution totheGasPhaseUsingtheESITechnique 134 5.3 DevelopingMethodstoStudyReactionMechanisms 135 5.3.1 MonitoringMethods 135 5.3.1.1 Off-LineMonitoring 135 5.3.1.2 On-LineMonitoring 136 5.3.2 Microreactors 136 5.3.2.1 PEEKMixingTeeasMicroreactor 136 5.3.2.2 CapillaryMixerAdjustableReactionChamber 137 5.3.2.3 PhotolysisCell 138 5.3.2.4 PhotochemicalReactor 139 5.3.2.5 NanosprayPhotochemicalApparatus 140 5.3.2.6 ElectrochemicalCell 141 5.4 ProbingReactivityofIntermediates 142 5.4.1 ReactionMechanismStudies 143 X Contents 5.4.1.1 RadicalFentonReaction 143 5.4.1.2 HeterogeneousFentonSystem 144 5.4.1.3 RadicalCationChainReactions 145 5.4.1.4 [2þ2]-CycloadditionofTrans-Anethole 145 5.4.1.5 ElectronTransferInitiatedDiels–AlderReactions 148 5.4.1.6 RadicalChainReactions 149 5.4.1.7 PhotochemicalReactions 151 5.4.1.8 PhotochemicalSwitchingReaction 151 5.4.1.9 PhotoinitiatedPolymerizationReaction 153 5.4.2 ElectrochemicalReactions 154 5.4.3 HeckReaction 154 5.4.4 SuzukiReaction 156 5.4.5 Pd-CatalyzedEnantioselectiveAllylationReaction 156 5.4.6 StilleReaction 157 5.4.7 AlkynilationofTelluridesMediatedbyPd(II) 158 5.4.8 LewisAcid-CatalyzedAdditions 162 5.4.9 C–HActivationandHydrogenations 162 5.4.10 OxidationReactions 163 5.4.11 Epoxidation 164 5.4.12 TheBaylis-HillmanReaction 166 5.4.13 TheBaylis-HillmanReactionCo-CatalyzedbyIonicLiquids 167 5.4.14 RingContractionReaction 169 5.4.15 NucleophilicSubstitutionReactions–TheMeisenheimer Complex 169 5.4.16 OxidativeDegradationofCaffeine 171 5.4.17 MimickingAtmosphericOxidationofIsoprene 173 5.4.18 a-MethylenationofKetoesters 175 5.4.19 TransientIntermediatesofPetasisandTebbeReagent 176 5.4.20 On-LineScreeningoftheZiegler–NattaPolymerization Reaction 178 5.4.21 On-LineScreeningoftheBrookhartPolymerizationReaction 181 5.4.22 TeCl AdditiontoPropargylAlcohols 181 4 5.4.23 MechanismofTröger'sBaseFormation 186 5.5 Conclusion 187 References 188 6 GasPhaseLigandFragmentationtoUnmaskReactive MetallicSpecies 199 RichardA.J.OHair 6.1 IntroductionandScopeoftheReview 199 6.2 UnmaskingReactiveMetallicIntermediatesviaCollision-Induced Dissociation 201 6.2.1 FormationandReactivityofOrganometallics 201 6.2.1.1 FormationandReactionsofOrganolithiumIons 202 6.2.1.2 FormationandReactionsofAlkalineEarthOrganometalates 203 Contents XI 6.2.1.3 FormationandReactionsofOrganocupratesand Organoargentates 205 6.2.1.4 FormationofMetalCarbenes 208 6.2.2 FormationandReactivityofMetalHydrides 210 6.2.2.1 MononuclearMetalHydrides 210 6.2.2.2 MultinuclearMetalHydrides 212 6.2.3 FormationandReactivityofMetalOxides 215 6.2.3.1 BondHeterolysis 215 6.2.3.2 BondHomolysisofMetalNitritesandNitrates 216 6.2.4 FormationandReactivityofMetalNitridesandRelatedSpecies 220 6.3 Conclusions 224 References 224 7 PalladiumIntermediatesinSolution 229 AnnaRoglansandAnnaPla-Quintana 7.1 Introduction 229 7.2 ESI-MSStudiesinSuzuki-MiyauraCross-Couplingand RelatedReactions 231 7.3 ESI-MSStudiesintheIdentificationofOxidativeAddition Intermediates 237 7.4 ESI-MSStudiesinMizoroki-HeckandRelatedReactions 240 7.5 ESI-MSStudiesinStilleCross-CouplingReactions 251 7.6 ESI-MSStudiesinPalladium-CatalyzedReactions InvolvingAllenes 254 7.7 ESI-MSStudiesinPalladium-CatalyzedAlkynylationReactions 258 7.8 ESI-MSStudiesinPalladium-CatalyzedAllylicSubstitution Reactions 260 7.9 ESI-MSStudiesinPalladium-CatalyzedOxidation of2-Allylphenols 268 7.10 ESI-MSStudiesinPalladium-CatalyzedPolymerizationReactions 269 7.11 Conclusions 272 References 273 8 PracticalInvestigationofMolecularandBiomolecularNoncovalent RecognitionProcessesinSolutionbyESI-MS 277 KevinA.Schug 8.1 Introduction 277 8.2 MethodsandApplications 280 8.3 PracticalAspectsofTitrationAnalysis 290 8.4 SummaryandOutlook 298 References 298 Index 307
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