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三联吡啶

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REVIEWSynthesisof′Substituted,′:′,′′TerpyridinesSynthesisof′Substituted,′:′,′′TerpyridinesRezaAliFallahpour*RolicResearchLtd,Gewerbestrasse,AllschwilFax()Email:RezaFallahpourrolicchReceivedOctoberrevisedNovemberSynthesis,No,Print:ArtIdX,E,,,,,ftx,enESSpdf©GeorgThiemeVerlagStuttgart·NewYorkISSNAbstract:Theterdentateligand,′:′,′′terpyridine(tpy)hasincreasinglybecomeoneofthemostpopularligandsincoordinationchemistryAvarietyofsubstituentsareutilisedtotailorthepropertiesofitsmetalcomplexes,′:′,′′TerpyridinewasreactedwithalmostalltransitionmetalstoformcomplexesAmongaseriesoftpyligandderivatives,thosecontainingsubstituentsattheC(′)positionareofespecialinterestMetalbondedtpyligandswithspacersatC(′)provideameansofdirectionality,andthusameansoflinearcommunication,itmeansthatelectroniccommunicationcanoccuralongthecoordinationaxisInaddition,theinsertionofasinglesubstituentattheC(′)positionofthetpyligandresultsinnoenantiomericderivatives,asthederivativeretainsitsplaneofsymmetryThesyntheticstrategiesusedtopreparetpyligandsarereviewedcomprehensivelyIntroductionTheConfigurationof,′:′,′′TerpyridineMethodsfortheSynthesisoftpyLigandsCondensationMethodologyPyrolysisofHydrazoniumSaltTohdaMethodologyMetalmediatedMethodologiesSauerMethodologySynthesisofLigands′AromaticSubstituted,′:′,′′terpyridinesSynthesisoftpyLigandsPossessingFunctionalGroupsDirectlyAttachedtoC(′)PreparationofTrimethylDerivativesof,′:′,′′TerpyridineCarbonylDerivativesoftpyLigandsSynthesisof′CarbaldehydeOxime,′:′,′′terpyridineCarboxylateDerivativesoftpyLigandsSynthesisof′Nitro,′:′,′′TerpyridinesSynthesisof′Hydroxy,′:′,′′terpyridinesSynthesisof′,′Bis(,′:′,′′terpyridyl)amineSynthesisof′Thiosubstituted,′:′,′′TerpyridinesSynthesisof,′:′,′′Terpyridine′oxidesConclusionKeywords:terpyridine,bipyrdine,oligopyridineoxide,couplingreaction,supramolecularchemistryIntroductionOligopyridineshaveattractedspecialinterestincoordinationchemistryAlthough,′bipyridine(bpy)wasannouncedas‘themostusedligandincoordinationchemistry’,,′:′,′′terpyridine(tpy)alsohasarichchemistryassociatedwithitAlmostyearsago,BurstallandMorganreportedthefirstsynthesisoftpy,ThecoordinationchemistryofthesubstitutedtridentateligandhasattractedmanychemistsLigandtpyhasbeenreactedwithverymanymetalstopreparecomplexesThekineticsandmechanismofformationofmetalcomplexesandtheirstabilityhavealsobeenstudied–Inthefieldofsupramolecularchemistrytpyhasfoundwideapplicationwhichhasledtotheformationofracks,ladders,grids,helicates,–catenanes,–knots,,anddendrimers–andasaresultoftheirchemicalandphotochemicalproperties,thesemetalcontainingcompoundshavebeenextensivelystudiedInparticular,thephotochemicalpropertiesofRu(bpy)specieshavebeenextensivelyinvestigatedwhichhasinitiatedinterestintheirrelatedcomplexesofthehigheroligopyridines,especiallyterpyridines–Thephotochemistryoftpymetalcomplexesisverywellinvestigated–Ascatalysts,tpycomplexesoftransitionmetalsareofspecialinterest,especiallythehigheroxidationstateoftransitionmetals,egRu(IV)orRu(VI),havefoundapplicationintheoxidationofalcohols,–asbleachingagents,–inthecarbonylationofaromaticcompounds,–inhydroformylationreactions–andasoxygenbindingmolecules,AninterestingaspectoftheircatalyticactivationistheseparationofAm(III)Eu(III)insolution,Chiralderivativesoftpyligandshavebeenprepared,–andappliedtoenantioselectivereactions–ortotheformationofhelicateswithtransitionmetals,–FunctionalisedtpyligandshavebeenanchoredtoTiOsurfaces,–goldsurfacesortosilicatitaniumsurfacestobuildmonolayersorsemiconductorsandtheirenergytransferpropertieshasbeeninvestigatedInthismannermetalclustersoftpyligandshavealsobeenprepared–Alsotpywaspolymerised,–andusedfordetectionoftransitionmetals,whilehelicalpolymershavealsobeenreportedPlatinum–andgold(III)complexesoftpyderivativeshavebeenappliedtobiologicalsystemsDerivativesoftpycanbelinkedtogetherbyspacersMetalbondedtpyligandswithspacersatC(′)provideameansofdirectionality,andthusameansoflinearcommunication,itmeans,theelectroniccommunicationcanoccuralongthecoordinationaxis(Figure)Inaddition,theinsertionofasinglesubstituentinthe′positionofthetpyligandresultsinnochangetothecentrosymmetricnatureandnoenantiomersform(contrastthiswithbpyDownloadedby:ShanghaiInstituteofOrganicChemistryCopyrightedmaterialRAFallahpourREVIEWSynthesis,No,–ISSN©ThiemeStuttgart·NewYorkderivatives)Therefore,thefunctionalisationoftpyatthispositionisofparticularimportanceFigureTheaimofthisarticleistocollectcomprehensivelythemethodsforthepreparationof′substitutedtpy’sMyintentionistoprovideasourceofpreparationoftpyforchemistwishingtoworkwithitHowever,IwouldliketolimitthisarticletothosetpyligandspossessingatleastonesubstituentattheC(′)positionTheConfigurationof,′:′,′′TerpyridineInthesolidstatethethreepyridineringsexhibittransoidconfigurationsabouttheinterannularcarboncarbonbonds(Figure)ThisconfigurationminimiseselectrostaticinteractionsbetweenthenitrogenlonepairsandalsotheVanderWaalsinteractionsbetweenHatomsarereducedWhenatpyligandisbondedtoametal,itcanisomerisetoacisconfiguration(Figure,b),butpreferablytociscisconfiguration(Figure,c)FigureIntpyderivatives,thethreepyridineringsareusuallyclosetobeingcoplanarTheinterplanaranglesofthetwoterminalringswiththecentralringaresimilarwithsamplevaluesof°(′phenyltpy),°(′dimethylaminotpy),°(′ethoxy,′′dimethyltpy)and°(,′′dibromo′phenyltpy)In′aminotpy,however,theinterplanaranglesofthetwoterminalringswiththecentralringare°and°,respectivelyThisdeviationfromtheexpectedanglesisduetohydrogenbondformation(Figure)SucheffectshavealsobeenobservedinothersimilarcompoundsFigure′AminotpyWhilealmostalltpyligandsareunsubstitutedatC()orC(′′),twoexamplesareknownpossessingsubstituentsatthesepositions–Duetosterichindrancethetwoterminalpyridineringsavoidthetransconfigurationandthistpyligandisassumedtoadoptthreedifferentisomersinvolvingππstackinginteractions(Figure)Thesituationchanges,however,whenthetpyligandisapartofanannulatedringsystemTwotypesofligandexist:a)theUshaped(Figure,g)andb)theSshapedone(Figure,h)IntheUshapedderivativesthecisconfigurationisfixed–RezaAliFallahpour(borninGhaemShahr,Iran,)andfinishedhighschoolinIran()InOctoberhemovedtoInnsbruck,Austria,wherehelearnedGermanandsubsequentlystudiedchemistryAfterreceivinghisdiploma()hejoinedProfessorHJHansen’sgroupattheUniversityofZurich,Switzerland()andobtainedhisPhD()AfteryearsofpostdoctoralresearchwithProfessorECConstableattheUniversityofBasel,Switzerland,hestartedhisownresearch(–)AttheendofhejoinedProfessorJHulliger’sGroupattheUniversityofBern,SwitzerlandInJanuaryhemovedthentoRolicResearchLtdinAllschwil,Switzerland,whereheiscurrentlyworkingBiographicalSketchDownloadedby:ShanghaiInstituteofOrganicChemistryCopyrightedmaterialREVIEWSynthesisof′Substituted,′:′,′′TerpyridinesSynthesis,No,–ISSN©ThiemeStuttgart·NewYorkFigureMethodsfortheSynthesisoftpyLigandsThetwogeneralmethodologiesusedinthesynthesisoftpyligandsinvolveeitherthesynthesisofthecentralring(Figure,i)orthecouplingofthethreepyridinerings(Figure,j)FigureFromthesyntheticpointofviewthereareonlyafewmethodsleadingtothissystemWhiletheUllmancoupling,ofbromopyridinesisofhistoricalinterest,themainmethodologiescanbedividedintothefollowingcategories:i)condensationmethodologyii)pyrolysisiii)Tohdamethodologyiv)metalmediatedcouplingreactionv)cycloaddition(Sauermethodology)CondensationMethodologyHantzschandTschitschibabininitiatedthefirsttwomethodsforpyridinesynthesisJamesonmethodologyManyattemptshavebeenmadetooptimisethepreparationoftpy,,–Maybethemostefficientmethodologyforthesynthesisoftpy()wasreportedbyJamesonandGuiseAcetylpyridine()wasreactedwithN,NdimethylformamidedimethylacetaltogivetheenaminoneinhighyieldThisenaminoneiscondensedwiththepotassiumsaltofacetylpyridine,lossofdimethylamine,resultsina,dione,whichisnotisolatedpriortoringclosurebyammoniumacetate(Scheme)SchemeReagentsandconditions:i)H(MeO)CNMeii)Potassiumacetylpyridinium,NHOAc–,HOAcoverallyield:KröhnkemethodologyStartingwiththeHantzschmethodology,variousmultistepsyntheticstrategieshavebeendevelopedtoimproveyieldsandproductspecificityKröhnkedevelopedcondensationmethodologyleadingtooligopyridinesThebasisofthisreactionisthealdolcondensationofacetylpyridine(orasubstitutedderivatives)withanaldehydeinbasicaqueousoralcoholicmediatogiveanα,βunsaturatedketoneorenoneMichaeladditionofasuitableenolatethenaffords,diketoneRingclosurewithammoniumacetateresultsintheformationofadihydropyridine,whichundergoesoxidationtothedesiredtpyAmajoradvantageofthisrouteisthatsymmetricalandunsymmetricaltpy’swerepreparedinmoderatetogoodyieldsThemaindisadvantageis,however,thatthesubstituentRmustbearomatic(Scheme)Inaddition,somefunctionalgroupsarenottoleratedunderthereactionconditionsUsingthismethodology,aseriesofcompoundspossessingaromaticsubstituentsatC(′)ofthetpyligandwerepreparedAnexcellentreviewhasalreadybeenpublisheddescribingtpyligandsattachedtoaromaticsusingthismethodologyRecently,thismethodologywasexaminedinsolventfreeonepotreactionsforthesynthesisofoligopyridines,PottsMethodologyPottsandcoworkershavealsodevelopedamethodologyforthesynthesisofsubstitutedpyridinesfromthecorresponding,dioneandhydroxylamineThoughinmanyaspectssimilartotheKröhnkemethodology,thisprocedurehasfoundwideapplicationsinthesynthesisofoligopyridines,especiallywhenC(′)issubstitutedbyathiolgroup(Scheme),Thereactionofthepotassiumenolateofacetylpyridine(orasubstitutedderivatives)withcarbondisulfidefollowedbymethyliodidegivesanαoxoketenedithioacetalReactionwithafurtherequivalentofthepotassiumenolateofacetylpyriFigureDownloadedby:ShanghaiInstituteofOrganicChemistryCopyrightedmaterialRAFallahpourREVIEWSynthesis,No,–ISSN©ThiemeStuttgart·NewYorkdine(orasubstitutedderivatives)affordsanenedioneintermediate,whichgivesafterinsituringclosurewithammoniumacetateinglacialaceticacidatrefluxTheadvantageofthismethodisthatsymmetricandunsymmetricaltpyligandscanbepreparedingoodyieldsAnexcellentreviewwasalreadypublishedbyPottsinSchemeReagentsandconditions:i)a)tBuOK,THFb)CSc)MeIii)N{(′pyridyl)oxoethyl}pyridiniumiodide,NHAcO–,CHCOOH:overallyield:–NewApproachAnewapproachwasadoptedforthesynthesisofsymmetricaltpy’s,thoughthismethodologyislimitedtotwoexamplesand(Scheme),Diacetylpyridine()wasquantitativelyconvertedto,bis(cyclohexylacetamidoyl)pyridine()byreactionwithcyclohexylamineinrefluxingbenzeneThetetrahydropyridineswereobtainedbycyclisationofthebisiminewithethylenetetramethyldisilylprotectedbromopropylaminesinexcellentyieldviaαalkylation,NdeprotectionandtransaminationThetetrachlorinationofwasaccomplishedbyreactionwithNchlorosuccinimide(NCS)incarbontetrachlorideatroomtemperatureThetetrachloroadductswerenotisolated,butimmediatelyconvertedbytheactionofsodiummethoxideinmethanolatroomtemperaturedirectlytothedesiredtpyligandsandDespiteeachstepresultinginhighyieldthismethodislong(steps)andverycostlySchemeReagentsandconditions:i)Cyclohexylamine,benzene,°C,h,ii)a)LDA,THF,°Cequiv,THF,°Cc)KCO,MeOH,°Cd)(HOC)inHO,overallyield:iii)a)NCS,CCl,rt,hb)MNaOMe–MeOH,°C,h,(),()PyrolysisofHydrazoniumSaltMethylacetylpyridine()wasreacteddirectlywithanhydrousN,NdimethylhydrazinetogivethecorrespondingN,NdimethyhydrazoneinyieldThequaternisationoftheaminefunctionalityofwithalcoholicmethyliodideaffordedthecorrespondingN,N,NtrimethylhydrazoniumiodidewhichwasthenconvertedtotheN,N,Ntrimethylhydrazoniumtetrafluoroborate()uponreactionwithsodiumfluoroborateThepyrolysisofat°Cgave,′′dimethyltpy()inyield(Scheme)Thoughthismethodwasextensivelyinvestigatedforthesynthesisofpyridinederivatives,intheseriesoftpyligands,onlycompoundwaspreparedbythismethodSchemeReagentsandconditions:i)MeNNH,catCHCOOH,EtOH,°C,h,ii)a)MeI,MeOH,h,b)NaBF,HO,°C,h,iii)°C,h,SchemeReagentsandconditions:i)RCHO,NaOH,EtOH,°C,–ii)N{(′pyridyl)oxoethyl}pyridiniumiodide,NHAcO–,EtOH:overallyield:–NONORNNNNNROORRRRRRRi)ii)NNOOSRNORNORSRRSNNNSRRRRRi)ii)Downloadedby:ShanghaiInstituteofOrganicChemistryCopyrightedmaterialREVIEWSynthesisof′Substituted,′:′,′′TerpyridinesSynthesis,No,–ISSN©ThiemeStuttgart·NewYorkTohdaMethodologyThereactionofelectrondeficientmethyl,dinitropyridone()withketonesoraldehydesinthepresenceofammoniagavealkylandorarylsubstitutednitropyridinesUponreactionofwith,diacetylpyridine(),,′′dinitrotpy()wasobtainedinyield(Scheme)SchemeReagentsandconditions:i)NH–MeOH,autoclave,°C,h,MetalmediatedMethodologiesMetalmediatedcouplingreactionshavefoundwideapplicationinorganicchemistryArelevantbookhasbeenpublishedExamplesappliedtothesynthesisofoligopyridinesarementionedbelowNickelmediatedReactionsThistypeofreactioniswidelyusedinthehomocouplingofaromaticcompoundswhileintheheterocyclicseriesithasnotfoundwideapplicationNickel()whichisproducedinsitubythereactionofNi(PPh)ClorevenbetterNi(PPh)Brwithmetalliczincisabletocoupletwoaromatichalogenides,preferablybromides,thoughsomechloridesarealsoreportedIntheseriesofthesynthesisoftpyligands,thoseligandspossessinghalogenatedaromaticsubstituentsatC(′)or′bromotpywerecoupledAmongseveralexamplesknown,onlyoneexampleisgiventodemonstratethismethodologyItshouldalsobementioned,thatonlysymmetricalligandscanbepreparedinthismanner(Scheme)SchemeReagentsandconditions:i)Ni(PPh)Cl,Zn,DMF,°C,h,PalladiummediatedReactionsThepalladiumcatalysedformationofcarboncarbonbondshasbeenextensivelystudiedBothtypesofcatalystpalladium(II)orpalladium()canbepreparedinsituThereactionsmaybepursuedeitherinorganicorinaqueousmediaAnexcellentreviewhasbeenpublishedSuzukiReactionTheSuzukicouplingreactioniscatalysedbyapalladium(II)compoundandtakesplacebetweenanaromaticboricacidandanaromatichalogenide,preferably,abromide(Scheme)ThesereactionsareveryusefulandtheyieldisnormallyhighThisreactionisusedmainlyinthecouplingofaromaticcompounds,thoughsomealkylbromideswerealsousedThismethodwasapplicabletothepreparationofbothsymmetricalandunsymmetricaltpyligandsSchemeReagentsandconditions:i)Pd(PPh),NaCO(aq),DME–EtOH,°C,h,StilleCouplingReactionTheStillecouplingreaction,whichconsistsofthereactionofstannylcompoundandbromocompoundinthepresenceofacatalyticamountofpalladium()andpalladium(II),respectively,hasfoundwideapplicationinthesynthesisofaromaticandheterocycliccompounds(Scheme)AnexcellentreviewarticlehasalreadybeenpublishedTheadvantageofthismethodisthatmanyfunctionalitiessuchasnitro,carboxylate,carbonyl,cyanogroupsorpyridineNoxidesarenotaffectedbythereactionconditionsSchemeReagentsandconditions:i)Pd(PPh),mxylene,°C,–d–AmajorconsiderationwhencarryingouttheworkupofreactionmixturesfromtheStillecrosscouplingistheremovaloftinbyproductsWhiletrimethyltinchlorideiswatersolubleandrathervolatile,tributyltinchloridehasalowvolatilityandissolubleinmostorganicsolventsSeparationonsilicagelisdifficultduetothetendencyoftributyltinchloridetoeluteundernonpolarconditions,andtostreakonthecolumnWefirstreportedtheeasyworkupoftheStillecouplingreaction,appliedtothesynthesisofoligopyrdines,–Onceoneisworkingwithbasiccompounds,egoligopyridines,however,theworkupismadeveryeasyWhilebasesaresolubleinconcentratedhydrochloricacid,thetinbyproductscanberemovedbyextractionwithdichloromethaneNeutralisationoftheNNNNNOONONOOONNOi)NSnRRNBrBrNRNBrabci)Downloadedby:ShanghaiInstituteofOrganicChemistryCopyrightedmaterialRAFallahpourREVIEWSynthesis,No,–ISSN©ThiemeStuttgart·NewYorkacidicaqueousphasewithaninorganicbase,usuallysodiumcarbonateorsodiumhydroxide,givesthefreeligandsTheorganiccompound,whichcontainsnotraceoftinbyproducts,canbe

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