偶聯(lián)反應(yīng)小結(jié)演示文稿

偶聯(lián)反應(yīng)小結(jié)演示文稿當前1頁，總共97頁。（優(yōu)選）偶聯(lián)反應(yīng)小結(jié).當前2頁，總共97頁。經(jīng)典反應(yīng)式當前3頁，總共97頁。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當前4頁，總共97頁。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)當前5頁，總共97頁。GeneralMechanism當前6頁，總共97頁。Kumada,Kumada-Corriu

Coupling1960年Chatt和Shaw:

1970年Uchino等:

當前7頁，總共97頁。Sp3C-Xsubstrate?當前8頁，總共97頁。當前9頁，總共97頁。配體的影響

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

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

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

AlkylDerivativesasSubstrate當前19頁，總共97頁。AlkylDerivativesasSubstrateTMEDAplaysacrucialroletoreduceβ-hydrideeliminationEntryaAdditiveProductYield(GC,%)CDEAF1None5790462Et3N37801153N-Methylmorpholine8720454DABCO20207535NMP153Trace7946TMEDA71193Trace10Nakamura,E.et.al.J.Am.Chem.Soc.

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

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

2004,69,3950.SynthesisofR-(+)-MuscopyridineandimmunosuppressiveagentFTY720當前21頁，總共97頁。Fürstner,A.et.al.Angew.Chem.Int.Ed.

2003,42,5358.SynthesisofLatrunculinB當前22頁，總共97頁。IndustrialexamplesHokkoChemicalIndustry,JapanScale:20t/ySolvent:FromEthertoTHF,withTolueneasco-solvent.當前23頁，總共97頁。當前24頁，總共97頁。當前25頁，總共97頁。Pd(PPh3)4TON74,000910,000環(huán)鈀催化劑PtBu328,000,000ArClsubstrateWatersoluble當前26頁，總共97頁。反應(yīng)底物有機硼酸（酯）ArBr經(jīng)格氏反應(yīng)，或者nBuLi，與B(OR)3反應(yīng)得到硼氫化反應(yīng)當前27頁，總共97頁。當前28頁，總共97頁。當前29頁，總共97頁。當前30頁，總共97頁。當前31頁，總共97頁。當前32頁，總共97頁。當前33頁，總共97頁。當前34頁，總共97頁。當前35頁，總共97頁。當前36頁，總共97頁。當前37頁，總共97頁。Losartan,Merck(1994),抗高血壓藥物JOC,1994,59,6391當前38頁，總共97頁。PharmaciaCo.andDow當前39頁，總共97頁。當前40頁，總共97頁?？拐婢鷦ゝungizideBoscalid,BASF,1000t/y當前41頁，總共97頁。Cancercellgrowthinhibitor,Novartis當前42頁，總共97頁。TreatmentforHIV當前43頁，總共97頁。Stille偶聯(lián),StilleCoupling當前44頁，總共97頁。SubstratesStille偶聯(lián)反應(yīng)中兩組份的組合

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