偶联反应小结演示文稿

偶联反应小结演示文稿当前1页，总共97页。（优选）偶联反应小结.当前2页，总共97页。经典反应式当前3页，总共97页。Cross-CouplingReactionsCatalystMRR'XKumada-Corriu(1972)NiorPdMgAryl,alkyl,vinylAryl,alkyl,vinylCl,Br,I,OTsSonogashira(1975)Pd/CuICuAryl,alkylAryl,alkyl,vinylBr,INegishi(1977)NiorPdZnAryl,allyl,benzyl,propargylAryl,alkyl,vinyl,alkynyl,benzyl,allylCl,Br,I,OTsStille(1978)PdSnAryl,vinyl,benzyl,alkynylAryl,alkyl,vinyl,benzyl,allyl,acylCl,Br,I,OTsSuzuki(1979)PdBAryl,alkylAryl,alkyl,alkynylCl,Br,I,OTsHiyama(1988)NiorPdSiArylAryl,alkyl,vinylBr,I,OTs当前4页，总共97页。Kumada,Suzuki,Stille,Negishi,Hiyamacoupling(C-CFormation：C-X+C-M)Buchwald-Hartwigcoupling(C-N,C-O,C-SFormation:C-X+Nu(N,O,S)-H)a-ArylationofKetone(C-CFormation:C-X+C-H)Heck,Sonogashiracoupling(AlkeneandalkyneFormation:C-X+C-H)当前5页，总共97页。GeneralMechanism当前6页，总共97页。Kumada,Kumada-Corriu

Coupling1960年Chatt和Shaw:

1970年Uchino等:

当前7页，总共97页。Sp3C-Xsubstrate?当前8页，总共97页。当前9页，总共97页。配体的影响

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1983,24,5449.Newdevelopmentofthecatalyst当前17页，总共97页。Arylchlorides,triflatesandtosylatesarebettersubstratesthanarylbromidesandiodidesEntryXYield(GC,%)ab1I27462Br38503Cl>95-4OTf>95-5OTs>95-Fürstner,A.et.al.Angew.Chem.Int.Ed.Engl.

2002,41,609.当前18页，总共97页。β-Hydrideeliminationandhomocouplingarethemajorsetbackwiththecross-couplingof1oand2oalkylsubstrateswitharylGrignardreagentsEntrySolventProductYield(%)CDEF*1THF/NMP252524262THF272720253Et2O601912124Et2O(reflux)691899Hayashi,T.et.al.Org.Lett.

2004,6,1297.*Amountafter0.05mmol(equivalenttocatalyst)subtracted.

AlkylDerivativesasSubstrate当前19页，总共97页。AlkylDerivativesasSubstrateTMEDAplaysacrucialroletoreduceβ-hydrideeliminationEntryaAdditiveProductYield(GC,%)CDEAF1None5790462Et3N37801153N-Methylmorpholine8720454DABCO20207535NMP153Trace7946TMEDA71193Trace10Nakamura,E.et.al.J.Am.Chem.Soc.

2004,126,3686.aPhMgBr(1.2equiv),additive(1.2equiv),30min.当前20页，总共97页。Fürstner,A.et.al.Angew.Chem.Int.Ed.

2003,42,308.Fürstner,A.et.al.J.Org.Chem.

2004,69,3950.SynthesisofR-(+)-MuscopyridineandimmunosuppressiveagentFTY720当前21页，总共97页。Fürstner,A.et.al.Angew.Chem.Int.Ed.

2003,42,5358.SynthesisofLatrunculinB当前22页，总共97页。IndustrialexamplesHokkoChemicalIndustry,JapanScale:20t/ySolvent:FromEthertoTHF,withTolueneasco-solvent.当前23页，总共97页。当前24页，总共97页。当前25页，总共97页。Pd(PPh3)4TON74,000910,000环钯催化剂PtBu328,000,000ArClsubstrateWatersoluble当前26页，总共97页。反应底物有机硼酸（酯）ArBr经格氏反应，或者nBuLi，与B(OR)3反应得到硼氢化反应当前27页，总共97页。当前28页，总共97页。当前29页，总共97页。当前30页，总共97页。当前31页，总共97页。当前32页，总共97页。当前33页，总共97页。当前34页，总共97页。当前35页，总共97页。当前36页，总共97页。当前37页，总共97页。Losartan,Merck(1994),抗高血压药物JOC,1994,59,6391当前38页，总共97页。PharmaciaCo.andDow当前39页，总共97页。当前40页，总共97页。抗真菌剂fungizideBoscalid,BASF,1000t/y当前41页，总共97页。Cancercellgrowthinhibitor,Novartis当前42页，总共97页。TreatmentforHIV当前43页，总共97页。Stille偶联,StilleCoupling当前44页，总共97页。SubstratesStille偶联反应中两组份的组合

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当前66页，总共97页。F-(TBAF)activatorneeded当前67页，总共97页。当前68页，总共97页。当前69页，总共97页。当前70页，总共97页。当前71页，总共97页。Hiyama-Denmarkcoupling当前72页，总共97页。当前73页，总共97页。当前74页，总共97页。Kosugi,1983当前75页，总共97页。当前76页，总共97页。当前77页，总共97页。当前78页，总共97页。当前79页，总共97页。当前80页，总共97页。当前81页，总共97页。当前82页，总共97页。当前83页，总共97页。当前84页