2015学术论坛有机分组13

望道项目14098复旦大学化学系2013级本科生李根指导教师：麻生明教授贾敏强研究员1钯催化的通过Negishicoupling类型反应制备多取代联烯

——通过配体调控β-H消除和还原消除的选择性背景介绍与课题设计条件选择与优化底物普适性研究机理研究总结致谢2内容背景介绍与课题设计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.条件选择与优化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底物普适性研究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机理讨论19

Rationaleforproposedmechanism2021Aphenomenonobservedinthisreaction22CO2atmosphereAratmosphereAphenomenonobservedinthisreaction1、对反应机理做更深入的研究（1）原位红外（δCO2=2365cm-1）（2）高分辨质谱2、尝试通过手性配体实现由外消旋底物制备轴手性联烯23FurtherresearchδCO2=？总结24Conclusion25感谢麻生明老师和贾敏强老师在科研和生活上对我的引导与帮助感谢缪不可言师兄对我的严格要求以及在课题上对我的帮助感谢复旦大学本科生学术研究计划望道项目(14098)的资助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--条件优化——溶剂、温度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条件优化——催化剂29条件优化——溶剂30EntrySOLVENTA(%)B(%)C(%)S.M.Recovery(%)1DMF--70-2THF--64-3tol--56-4Dioxane--62-5Et2O--54-6hex--43-7DCM--56-8CH3CN--42-31条件优化——溶剂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条件优化——催化剂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-条件优化——催化剂33EntrybaseA(%)B(%)C(%)S.M.Recovery(%)1tBuOK--trace-2tBuONa--trace-3tBuOLi--41-4pyrrole--62-5Et3N--56-6py--54-8K2CO3--76-条件优化——碱34EntrybaseA(%)B(%)C(%)S.M.Recovery(%)9KH2PO4--71-10NaHSO4·H2O--72-11Na