2015學(xué)術(shù)論壇有機分組13

望道項目14098復(fù)旦大學(xué)化學(xué)系2013級本科生李根指導(dǎo)教師：麻生明教授賈敏強研究員1鈀催化的通過Negishicoupling類型反應(yīng)制備多取代聯(lián)烯

——通過配體調(diào)控β-H消除和還原消除的選擇性背景介紹與課題設(shè)計條件選擇與優(yōu)化底物普適性研究機理研究總結(jié)致謝2內(nèi)容背景介紹與課題設(shè)計34Thedesignoftheresearch5Background6TheapplicationofallenesSchreiber,S.L.;Kiessling,L.L.J.Am.Chem.Soc.

1988,53,1623.Ma,S.;Lu,P.;Lu,L.;Hou,H.;Wei,J.;He,Q.;Gu,Z.;Jiang,X.;Jin,X.Angew.

Chem.Int.Ed.2005,44,52757ATAreaction(allenylationofterminalalkynes)Crabbé,P.;André,D.;Fillion,H.TetrahedronLett.1979,20,893.Nakamura,H.;Sugiishi,T.;Tanaka,Y.TetrahedronLett.2008,49,7230.Kuang,J.;Ma,S.J.Org.Chem.

2009,74,1763.Kuang,J.;Ma,S.J.Am.Chem.Soc.

2010,132,1786.Kuang,J.;Luo,H.;Ma,S.Adv.Synth.Catal.2012,354,933.Kuang,J.;Xie,X.;Ma,S.Synthesis2013,45,592.Ye,J.;etal.Ma,S.Org.Lett.

2012,14,1346.Zhang,J.;Ye,J.;Ma,S.Org.Biomol.Chem.2015,13,4080.Ye,J.;Lü,R.;Fan,W.;Ma,S.Tetrahedron2013,69,8959.Lü,R.;etal.Ma,S.Org.Lett.

2013,15,2254.Ye,J.;Fan,W.;Ma,S.,Chem.Eur.J.2013,19,716.Huang,X.,Cao,T.,Han,Y.,Jiang,X.,Lin,W.,Zhang,J.,Ma,S.Chem.Commun.2015,51,6956.X.Tang,X.Huang,etal,S.Ma,Org.Chem.Front.2015,2,688.條件選擇與優(yōu)化8EntryLigandYieldofA(%)YieldofB(%)YieldofC(%)S.M.Recovery(%)1L19432-2L225441-3L38trace33-4L43935-5L5-328-6L68841-7L79437-8L821738-9SPhostrace86trace-Optimizationofthereactionconditions9EntryLigandYieldofA(%)YieldofB(%)YieldofC(%)S.M.Recovery(%)10XPhos8343-11tBuXPhos9639-12Zheda-Phos932813LBPhos7544-14Gorlos-Phostracetrace57-15SegPhos-27-5316BINAP-923-17XantPhos-4012-18DPPF8727-10OptimizationofthereactionconditionsEntryLigandYieldofA(%)YieldofB(%)YieldofC(%)S.M.Recovery(%)19DPPM87231120DPPE---8821DPPP---8722DPPB---86231,10-Phen6335-242,2’-bpy8233-25iPr-PHOX8735-26L95235-27L10tracetrace15-28L115443-11OptimizationofthereactionconditionsEntryCat.LigandbaseSolventTemp.(oC)2(%)3(%)

1Pd(OAc)2Gorlos-PhosKOHDMF25-57

2Pd(OAc)2Gorlos-PhosDMF25-trace3Pd(OAc)2Gorlos-PhosEt3NDMF25-464Pd(OAc)2Gorlos-PhosK2CO3DMF25-615Pd(TFA)2Gorlos-PhosK2CO3DMF25-706Pd(TFA)2Gorlos-PhosK2CO3Hexane25-437Pd(TFA)2Gorlos-PhosK2CO3NMP25-758Pd(TFA)2Gorlos-PhosK2CO3NMP0-829Pd(TFA)2Gorlos-PhosK2CO3NMP45-6510Pd(OAc)2SPhos-DMF2586-12OptimizationofthereactionconditionstBuONa底物普適性研究1314AninterestingphenomenonEntryR1R2Yieldof2[a]

(%)Yieldof3[a]

(%)withCO2withoutCO2withCO2withoutCO21nBuPh877681742nBup-Tol857580753nBuα-Nap856872654PhPh78776665Substratescope15EntryR1R2Yieldof2[a]

(%)Yieldof3[a]

(%)withCO2withoutCO2withCO2withoutCO25nBu2,4-dicholorphenyl727285836nBup-MeOOCC6H4676670677nBum-O2NC6H457complicated60458nBup-NCC6H4757558589nBup-ClC6H48681807610nBup-CF3C6H47479727611bnBuPh85-80-16Substratescope[a]isolatedyield[b]gram-scale

reaction17Substratescope18Entry

ZnR12XCO2(isolatedyield)Ar(isolatedyield)23231ZnMe2OCOOMe90-89-2ZnPh2

OCOOMe86-58-3ZnEt2OAc97918378Substratescope機理討論19

Rationaleforproposedmechanism2021Aphenomenonobservedinthisreaction22CO2atmosphereAratmosphereAphenomenonobservedinthisreaction1、對反應(yīng)機理做更深入的研究（1）原位紅外（δCO2=2365cm-1）（2）高分辨質(zhì)譜2、嘗試通過手性配體實現(xiàn)由外消旋底物制備軸手性聯(lián)烯23FurtherresearchδCO2=？總結(jié)24Conclusion25感謝麻生明老師和賈敏強老師在科研和生活上對我的引導(dǎo)與幫助感謝繆不可言師兄對我的嚴(yán)格要求以及在課題上對我的幫助感謝復(fù)旦大學(xué)本科生學(xué)術(shù)研究計劃望道項目(14098)的資助Acknowledge2627Thanksforlistening!EntrySolventTemp.A(%)B(%)C(%)S.M.Recovery(%)1NMP25-85--2DMA25-65--3DMF25-86--4THF25-71--5DME25-78--6CH3CN25-54--7toluene25-71--8DMF45-68--9DMF70-67--條件優(yōu)化——溶劑、溫度28Entry[Pd]Yield(%)1Pd(OAc)2862Pd(TFA)2803PdCl2614Pd(acac)2825Pd(Ph3P)433ofb-Heliminationproduct6Pd2(dba)3-CHCl3857[Pd(2-methyl-p-allyl)Cl]2818[Pd(cinnmyl)Cl]283條件優(yōu)化——催化劑29條件優(yōu)化——溶劑30EntrySOLVENTA(%)B(%)C(%)S.M.Recovery(%)1DMF--70-2THF--64-3tol--56-4Dioxane--62-5Et2O--54-6hex--43-7DCM--56-8CH3CN--42-31條件優(yōu)化——溶劑EntrySOLVENTA(%)B(%)C(%)S.M.Recovery(%)9NMP--78-10DMI--69-11DME--60-12DMA--75-13DMPU--76-14DMSO--73-Entrycat.A(%)B(%)C(%)S.M.Recovery(%)1[Pd(pi-allyl)Cl]2

--65-2Pd(OAc)2--71-3Pd(acac)2--58-4Pd2(dba)3·CHCl3--67-5Pd(TFA)2--78-6Pd(dmdba)2--72-dmdba條件優(yōu)化——催化劑32Entrycat.A(%)B(%)C(%)S.M.Recovery(%)7Pd(Ph3P)2Cl2--52-8PdCl2--68-9PdCl2(PhCN)2--24-10Pd(Ph3P)4--41-5Pd(TFA)2--78-條件優(yōu)化——催化劑33EntrybaseA(%)B(%)C(%)S.M.Recovery(%)1tBuOK--trace-2tBuONa--trace-3tBuOLi--41-4pyrrole--62-5Et3N--56-6py--54-8K2CO3--76-條件優(yōu)化——堿34EntrybaseA(%)B(%)C(%)S.M.Recovery(%)9KH2PO4--71-10NaHSO4·H2O--72-11Na