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按一下以編輯母片標題樣式,按一下以編輯母片,第二層,第三層,第四層,第五層,*,Microwave Assisted Organomolybdenum Lewis Acid Catalyzed Mukaiyama Aldol Reactions,Student:,Wanchen Lee,Supervisor:,Prof.Shuchun,Joyce Yu,2005/07/28,Department of Chemistry&Biochemistry,Chung Cheng University,1,Microwave Assisted Organomolyb,Mukaiyama Reaction,Silyl enol ether,Ketone or Aldehyde,Mukaiyama,T.et.al.,Chem.Lett.,1973,1011-1014,2,Mukaiyama Reaction Silyl enol,Lewis Acid Catalyzed Mukaiyama Reactions,I.,Traditional Lewis Acids,BF,3,O(Et),2,、,AlCl,3,、,InCl,3,、,SnCl,4,、,TiCl,4,、,FeCl,3,、,ZSM-5,II.,Organometallic Lewis Acids,a.Early Transition Metals,:Sc(III),、,V(IV),、,W(0),Chen,C.T.et.al.,Synlett.,1999,816-818,Loh,T.P.et.al.,Chem.Commun.,1996,1819-1820,Saigo,K.et.al.,Chem.Lett.,1974,323-326,Kobayashi,S.et.al.,Tetrahedron Lett.,1997,26,4559-4562,1-methyl imidazole,Mukaiyama,T.et.al.,Chem.Lett.,1973,1011-1014,Sasidharan,M.et.al.,Chem.Lett.,2003,32,624-625,Takeshi,O.et.al.,Tetrahedron Lett,.,2002,43,8959-8962,3,Lewis Acid Catalyzed Mukaiyama,b.Late Transition Metals:Fe(II),、,Ru(II),、,Cu(II),Chem.Commun.,1992,1634,Bosnich,B.et.al.,Tetrahedron Lett.,1992,39,5729-5732,Kobayashi,S.et.al.,Tetrahedron,1999,55,8739-8746,Kobayashi,S.et.al.,Green Chem.,1999,4,175-177,4,b.Late Transition Metals:Fe,III.,Lanthanide Metal Triflate(OTf)Complexes:,Yb(III),、,La(III),、,Pr(III),、,Nd(III),、,Sm(III),、,Eu(III),、,Gd(III),、,Dy(III),、,Ho(III),、,Er(III),Kobayashi,S.et.al.,J.Org.Chem.,1994,13,3590-3596,Kobayashi,S.et.al.,Tetrahedron Lett.,1997,26,4559-4562,5,III.Lanthanide Metal Triflate,IV.,Non-Metallic Catalysts,a.PS-Formamide,b.Ionic liquids,c.Brnsted acid,ex:citric acid and benzolic acid,d.Lewis base,ex:lithium acetate,、,potassium acetate and sodium acetate,Ogawa,C.;Sugiura,M.;Kobayashi,S.,Chem.Commun.,2003,192-193,Chen,S.L.;Ji,S.J.;Loh,T.P.,Tetrahedron Lett,.,2004,375-377,Li,G.L.;Zhao,G.,J.Org.Chem.,2005,70,4272-4278,Mukaiyama,T.;Kawano,Y.;Fujisawa,H.,Chem.Lett,.,2005,34,88-89,6,IV.Non-Metallic CatalystsOgaw,Solvent Systems for Mukaiyama Reactions,II.,Mixed Solvent System,EtOH-H,2,O,、,THF-H,2,O,I.,Molecular Organic Solvents,CH,2,Cl,2,、,CH,3,NO,2,、,CH,3,CN,、,DMF,III.,Green Solvents,R.T.Ionic Liquids(BmimPF,6,),Water,7,Solvent Systems for Mukaiyama,Indium Trichloride Catalyzed Mukaiyama Aldol Reaction in Water,Loh,T.P.et.al.,Chem.Commun.,1996,1819-1820,8,Indium Trichloride Catalyzed M,Sc(OTf),3,-Catalyzed Aqueous Aldol Reaction in Micellar Systems,Kobayashi,S.et.al.,Tetrahedron Lett.,1997,26,4559-4562,9,Sc(OTf)3-Catalyzed Aqueous Ald,Oxovanadium(IV)Biphenolate,Catalyzed,Mukaiyama,Aldol Reaction,Chen,C.T.et.al.,Synlett.,1999,816-818,10 mol%,L=1-methyl imidazole,10,Oxovanadium(IV)Biphenolate Ca,Ru(salen)(NO)H,2,OSbF,6,Catalyzed Mukaiyama Aldol Reaction,Bosnich,B.et.al.,Tetrahedron Lett.,1992,39,5729-5732,11,Ru(salen)(NO)H2OSbF6 Catalyz,Lewis Acid-Surfactant Combined Catalyst Systems,Kobayashi,S.et.al.,Green Chem.,1999,4,175-177,20 mol%,(10 mol%),12,Lewis Acid-Surfactant Combined,Lanthanide Triflate as Water-Tolerant Lewis Acid,Kobayashi,S.et.al.,J.Org.Chem.,1994,13,3590-3596,13,Lanthanide Triflate as Water-T,Polystyrene Supported Formamide Catalyzed Mukaiyama Aldol Reaction,Ogawa,C.;Sugiura,M.;Kobayashi,S.,Chem.Commun.,2003,192-193,14,Polystyrene Supported Formamid,Ionic Liquid Catalyzed Mukaiyama Aldol Reaction,Loh,T.P.et.al.,Tetrahedron Lett,.,2004,45,375-377,15,Ionic Liquid Catalyzed Mukaiya,Motivation,I.,Traditional Lewis acids are difficult to handle,II.,Lanthanide metals are relatively expensive,III.,Low Oxidation State Transition Metals,a.Relatively high moisture and oxygen stability,b.Inexpensive,c.Tunable electronic and steric environments around metal Lewis,acid center,IV.,Green Chemistry,a.Green solvents,R.T.ionic liquids(BmimPF,6,)and H,2,O,b.Energy saving,Catalysis under microwave irradiation,16,MotivationI.Traditional Le,Preparation of Organomolybdenum Catalyst,Thermal Conditions,17,Preparation of Organomolybdenu,Microwave Flash Heating Conditions,18,Microwave Flash Heating Condi,Crotonaldehyde-Lewis Acid Adduct,Childs,R.F.et.al.,Can.J.Chem,.1982,60,801,19,Crotonaldehyde-Lewis Acid Addu,chemical,shift,diff.,Lewis acid,on H,3,(ppm),BBr,3,1.49,AlCl,3,1.23,OP(2-Py),3,W(CO)(NO),2,(SbF,6,),2,1.23,OP(2-Py),3,W(CO)(NO),2,(BF,4,),2,1.22,OP(2-Py),3,W(CO)(NO),2,(SbF,6,),2,1.21,HOC(2-Py),3,W(CO)(NO),2,(SbF,6,),2,1.19,P(2-Py),3,W(CO)(NO),2,(BF,4,),2,1.18,BF,3,1.17,AlEtCl,2,1.15,HC(2-Py),3,Mo(CO)(NO),2,(SbF,6,),2,1.05,TiCl,4,1.03,P(2-Py),3,Mo(CO)(NO),2,(BF,4,),2,1.01,O,P(2-Py),3,Mo(CO)(NO),2,(BF,4,),2,0.992,Me,3,P(CO),3,(NO)W,+,0.93,SnCl,4,0.87,CpMo(CO),2,+,(PF,6,),0.70,Et,3,Al,0.63,CpFe(CO),2,+,BF,4,0.54,20,Organomolybdenum Lewis Acid Catalyzed Mukaiyama Aldol Reactions under Thermal Conditions,21,Organomolybdenum Lewis Acid Ca,Entry R R Yield(%),CH,3,CN DMF,1,65,72,2,99,83,3,61,77,4,79,77,5,59,76,6,59,64,22,Entry R,Entry R R Yield(%),CH,3,CN DMF,7,89,97,8,96,94,9,98,96,10,45,DMF:3.82 ;36.7,CH,3,CN:3.92 ;37.5,24,EntryRRYield(%)EntryRRYield,Entry R R Yield(%),1,43,72,28,2,99,85,62,3,77
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