链接化学与聚合 相关内容.docx

链接化学与聚合 相关内容.docx

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链接化学与聚合相关内容

Prof.K.B.Sharpless,Prof.M.G.Finn

DepartmentofChemistry

TheScrippsResearchInstitute

10550NorthTorreyPinesRoad

LaJolla,CA92037（USA）

Fax:

（+1）858-784-7562

E-mail:

sharples@scripps.edu

Dr.H.C.Kolb

VicePresidentofChemistry

CoelacanthCorporation

EastWindsor,NJ08520（USA）

JournalofPolymerScience:

PartA:

PolymerChemistry,Vol.44,5699–5707（2006）

ABC-TypeHetero-ArmStarTerpolymersThrough“Click”Chemistry

链接所需含炔化合物，同时含有ATRP引发剂、TEMPO引发剂

60oCATRPMMA聚合、125oCTEMPOSt聚合

80oCATRPtBA聚合、末端转化成叠氮功能基

单羟基聚乙二醇PEG、对甲苯磺酰氯，将末端转化成对甲苯磺酰基，再转化成叠氮功能基

三臂不同聚合物主链的星型聚合物

JournalofPolymerScience:

PartA:

PolymerChemistry,Vol.44,6458–6465（2006）

A3-TypeStarPolymersviaClickChemistry

AnalyticalChemistry,Vol.78,No.14,July15,20064969-4975

“ClickChemistry”inthePreparationofPorousPolymer-BasedParticulateStationaryPhasesforμ-HPLCSeparationofPeptidesandProteins

Thecopper（I）-catalyzed（3+2）azide-alkynecycloaddition,anelementofthe“clickchemistry”popularizedbySharpless’group,7isaveryefficientcouplingreactionthatprovidesanidealreactivityprofileforthispurpose.Equation1showsageneralschemeoftheCu（I）-catalyzedreactionofaterminalalkynewithaterminalazideaffordinga1,4-disubstitutedtriazolering:

Cu（I）催化的[3+2]叠氮-炔烃环加成是Sharpless研究小组广泛应用的链接化学的重要反应，是非常有效的偶联反应，能够保证理想的反应活性满足研究目的。

该反应在有机化学中是1,4-二取代三唑环的合成方法，原料是末端炔烃和末端叠氮化合物。

Thisreactionhasalreadybeenwidelyusedforthesynthesisofsubstitutedtriazolesinsolution.8-12Becauseazideandalkynefunctionalitiesdonotinterferewithcommonbiologicalprocesses,thecopper-catalyzedazide-alkynecycloadditionhasbeenusedforprofilingenzymeactivity13-17andtoincorporatenewfunctionalitiesinproteins,18cells,19andviruses.20This“click”reactionwasalsoappliedforthepreparationandfunctionalizationofdendrimers21,22aswellasforthesynthesis23andmodification24oflinearpolymers.Inaddition,theutilityofthisreactionhasalsobeendemonstratedinchemicalmodificationsperformedonsolidpolymersupports.Forexample,ithasbeenintegratedwithsolidphasepeptidesynthesistoproducepeptidotriazoles25,26andfortheinstallation,viaa“clicklinker”,ofsensitivefunctionalitiesonMerrifieldresinforsolid-phaseorganicsynthesis.27,28Finally,Punaetal.haverecentlypreparedanazidederivativeofdiaminodipropylamineagarosebeadsandusedthisclickreactiontoimmobilizealkyne-containingversionsofbiotinandahexapeptide.29Theyalsousedacomplementaryalkynederivativeofagarosetoattach4-azido-N-（4-（4-oxobutoxy）phenyl）butyramide;thisaldehydecontainingligandwasthenusedfortheselectiveseparationofaspecificantibody.

Chem.Commun.,2005,4333–4335

Click-chemistryasanefficientsynthetictoolforthepreparationofnovelconjugatedpolymers{

Chem.Commun.,2005,4581–4583

Efficientmicrowave-assistedsynthesisofmultivalentdendrimericpeptidesusingcycloadditionreaction（click）chemistry

Chem.Commun.,2006,4010–4012

Synthesisofstar-shapedpoly（ε-caprolactone）via‘click’chemistryand‘supramolecularclick’chemistry

Chem.Commun.,2006,3933–3935

Functionalizationofpolymerswithphosphorescentiridiumcomplexesviaclickchemistry

Chem.Commun.,2006,5051–5053

RAFTandclickchemistry:

Aversatileapproachtowell-definedblockcopolymers

近乎对称的三唑环链接的RAFT聚合所得聚苯乙烯

BioconjugateChem.2007,18,263-267

SolubleCamptothecinDerivativesPreparedbyClickCycloadditionChemistryonFunctionalAliphaticPolyesters

喜树碱（可用于癌症的治疗）

Sn（II）-mediatedring-openingcopolymerizationofα-propargyl-δ-valerolactoneandε-caprolactonewasconductedtogivealiphaticpolyester1withanearly1:

1ratioofthetwomonomers,asconfirmedbyintegrationofthe1HNMRspectrumofthepolymer.Gelpermeationchromatographyofpolyester1,performedinTHFagainstpolystyrenemolecularweightstandards,gaveanestimatednumber-averagemolecularweight（Mn）of9200g/molandapolydispersityindex（PDI,Mw/Mn）of1.17.

Synthesisof6-AzidohexanoicAcid

（2）.6-Bromohexanoicacid（5.0g,25.6mmol）andsodiumazide（8.37g,128mmol）weredissolvedinDMSOandstirredatroomtemperaturefor8h.ThereactionmixturewasthendissolvedinCH2Cl2,washedwithwater,brine,andNaHCO4（aq）,driedoverMgSO4,andconcentratedbyrotaryevaporation.ResidualDMSOwasremovedbyKugelrohrdistillationat120°C.Distillationat160°Cgave6-azidohexanoicacid2asacolorlessliquid（2.98g,74%）.MS-ESI（m/z）:

[M+Na]+calculatedforC6H11N3O2180.1,found180.1.1HNMR（CDCl3,300MHz）:

ä（CHCl3）7.26ppm）11.43（br,1H,COOH）,3.28（t,2H,CH2N3）,2.38（t,2H,CH2COOH）,1.65（m,4H,CH2CH2CH2CH2CH2）,1.43（m,2H,CH2CH2CH2CH2CH2）ppm.13CNMR（CDCl3,75MHz）:

ä（CHCl3）77.0ppm）180.1（CdO）,51.2（CH2N3）,33.9（CH2COOH）,28.5（CH2CH2N3）,26.2（CH2CH2CH2N3）,24.2（CH2CH2COOH）ppm.IR（ATR）:

NdNdN2090cm-1.

BioconjugateChem.2007,18,579-584

SynthesisofSymmetricalandUnsymmetricalPAMAMDendrimersbyFusionbetweenAzide-andAlkyne-FunctionalizedPAMAMDendrons

Biomacromolecules2006,7,3104-3111

“Clickable”PEG-DendriticBlockCopolymers

Biomacromolecules2007,8,744-749

Surface-Initiated,AtomTransferRadicalPolymerizationofOligo（ethyleneglycol）MethylEtherMethacrylateandSubsequentClickChemistryforBioconjugation

DesignedMonomersandPolymers,Vol.8,No.6,pp.533–546（2005）

Characterizationofα,ω-dihydroxypolystyrenebygradientpolymerelutionchromatographyandtwo-dimensionalliquidchromatography

Angew.Chem.Int.Ed.2006,45,5292–5296

“Click”ChemistrybyMicrocontactPrinting

Angew.Chem.Int.Ed.2001,40,2004-2021

ClickChemistry:

DiverseChemicalFunctionfromaFewGoodReactions

JournalofPolymerScience:

PartA:

PolymerChemistry,Vol.42,4392–4403（2004）

ClickChemistryinMaterialsSynthesis.1.AdhesivePolymersfromCopper-CatalyzedAzide-AlkyneCycloaddition

JournalofPolymerScience:

PartA:

PolymerChemistry,Vol.44,5513–5518（2006）

ClickChemistryinMaterialsSynthesis.II.Acid-SwellableCrosslinkedPolymersMadebyCopper-CatalyzedAzide–AlkyneCycloaddition

MolecularImagingVol5,No.2,April-June2006,pp.22-128

“Clickable”NanoparticulesforTargetedImaging

Macromol.RapidCommun.2005,26,514–518

CombiningAtomTransferRadicalPolymerizationandClickChemistry:

AVersatileMethodforthePreparationofEnd-FunctionalPolymers

JournalofPolymerScience:

PartA:

PolymerChemistry,Vol.44,5203–5217（2006）

FacileSynthesesofSurface-FunctionalizedMicellesandShellCross-LinkedNanoparticles

Chem.Eur.J.2006,12,6776–6786

Fluorogenic1,3-DipolarCycloadditionwithintheHydrophobicCoreofaShellCross-LinkedNanoparticle

J.AM.CHEM.SOC.2004,126,15020-15021

DendronizedLinearPolymersvia“ClickChemistry”

J.AM.CHEM.SOC.2006,128,4823-4830

SynthesisofNeoglycopolymersbyaCombinationof“ClickChemistry”andLivingRadicalPolymerization

J.AM.CHEM.SOC.2006,128,9318-9319

AssemblyofUltrathinPolymerMultilayerFilmsbyClickChemistry

J.AM.CHEM.SOC.2006,128,11356-11357

TowardtheSynthesesofUniversalLigandsforMetalOxideSurfaces:

ControllingSurfaceFunctionalitythroughClickChemistry

J.AM.CHEM.SOC.2005,127,14942-14949

OrthogonalApproachestotheSimultaneousandCascadeFunctionalizationofMacromoleculesUsingClickChemistry

J.AM.CHEM.SOC.2006,128,6564-6565

SynthesisofDegradableModelNetworksviaATRPandClickChemistry

J.AM.CHEM.SOC.2006,128,11360-11361

Synthesisof3-MiktoarmStarsand1stGenerationMiktoDendriticCopolymersby“Living”RadicalPolymerizationand“Click”Chemistry

J.AM.CHEM.SOC.2006,128,12084-12085

AVersatileNewMonomerFamily:

Functionalized4-Vinyl-1,2,3-TriazolesviaClickChemistry

Macromol.RapidCommun.2007,28,15–54

‘Click’ChemistryinPolymerandMaterialsScience

JournalofPolymerScience:

PartA:

PolymerChemistry,Vol.44,5699–5707（2006）1

JournalofPolymerScience:

PartA:

PolymerChemistry,Vol.44,6458–6465（2006）2

AnalyticalChemistry,Vol.78,No.14,July15,20064969-49753

Chem.Commun.,2005,4333–43354

Chem.Commun.,2005,4581–45834

Chem.Commun.,2006,4010–40125

Chem.Commun.,2006,3933–39356

Chem.Commun.,2006,5051–50537

BioconjugateChem.2007,18,263-2678

BioconjugateChem.2007,18,579-5849

Biomacromolecules2006,7,3104-311110

Biomacromolecules2007,8,744-74910

DesignedMonomersandPolymers,Vol.8,No.6,pp.533–546（2005）11

Angew.Chem.Int.Ed.2006,45,5292–529611

Angew.Chem.Int.Ed.2001,40,2004-202112

JournalofPolymerScience:

PartA:

PolymerChemistry,Vol.42,4392–4403（2004）13

JournalofPolymerScience:

PartA:

PolymerChemistry,Vol.44,5513–5518（2006）14

MolecularImagingVol5,No.2,April-June2006,pp.22-12815

Macromol.RapidCommun.2005,26,514–51815

JournalofPolymerScience:

PartA:

PolymerChemistry,Vol.44,5203–5217（2006）16

Chem.Eur.J.2006,12,6776–678617

J.AM.CHEM.SOC.2004,126,15020-1502117

J.AM.CHEM.SOC.2006,128,4823-483018

J.AM.CHEM.SOC.2006,128,9318-931919

J.AM.CHEM.SOC.2006,128,11356-1135719

J.AM.CHEM.SOC.2005,127,14942-1494919

J.AM.CHEM.SOC.2006,128,6564-656520

J.AM.CHEM.SOC.2006,128,11360-1136120

J.AM.CHEM.SOC.2006,128,12084-1208521

Macromol.RapidCommun.2007,28,15–5422