1、Transition Metal-Catalyzed C-H Bond Activation of Aromatic Compounds：Chelation-Assisted Ortho-Functionalization OutlineOutline Introduction Catalytic Ortho-Functionalization Conclusion and OutlookIntroductionIntroductionDGHtransition metal catalystDGFGDG=directing groupFG=functional groupRRIntroduct
2、ionIntroductionOH+C2H4RuOHOH+THF,177 C,KOPh75%13%RuPP(OPPh)3PP(OPh)3OPhPOORu=PhPOOPPhOPPhLewis,L.N.;Smith,J.F,J.Am.Chem.Soc.1986,108,2728IntroductionIntroductionR1OR2+Y2 mol%RuH2(CO)(PPh3)3toluene,refluxR1OR2YY=H,t-Bu,Si(OEt)3,CH2SiMe3,Ar66-100%OO100%96%SiMe3OSi(OEt)3100%OSi(OEt)3100%OOSi(OEt)3100%M
3、urai,S.;et al.Nature 1993,366,529IntroductionIntroductionORuORuORuHORuSiMe3SiMe3OSiMe3AdvantagesAdvantages High selectivity Atom economy Clean and economical process Catalytic Ortho-FunctionalizationCatalytic Ortho-Functionalization Ortho-Alkylation Ortho-Arylation Ortho-Carbonylation OthersOrtho-Al
4、kylationOrtho-AlkylationR1NPh+R3R2(1)2 mol%Rh(PPh3)3Cl toluene,150 C,2h(2)H3O+R1OR2R3R1=Me,Et,n-PentR2=CF3,H,CH3OR3=alkyl,aryl,silylup to 97%Jun,C.H.Angew.Chem.Int.Ed.2000,39,3440Ortho-AlkylationOrtho-AlkylationHNPhOMeOO(1)10 mol%Rh(coe)2Cl2 20 mol%FcPCy2 toluene,150 C,2h(2)H3O+HOMeOOOFcPCy2=FePCy2H
5、OMeOOOMeOOONH2HCl65%Ahrendt,K.A.;et al.Org.Lett.2003,5,1301Ortho-AlkylationOrtho-AlkylationHNBn(1)5 mol%Rh(coe)2Cl215 mol%ligand,tolueneHNBnOP N(CHCH3Ph)2ligand94%95%eeHNBnPh96%90%eeHNBnN90%70%eeHNBnO95%96%eeOThalji,R.K.;et al.J.Am.Chem.Soc.2004,126,7192Ortho-AlkylationOrtho-AlkylationNXHRB(OH)2/Ag2
6、O or Ag2CO3or methylboroxine/Cu(OAc)2cat Pd(OAc)2benzoquinone,airNXRR=Me,Et,n-Bu,n-Hex,Ph(CH2)2,cyclopropylNOBOBOBMeMeMePdIINOBOBOBMeMeMePdIIintramolecular transmatalationNMeChen X.;et al.J.Am.Chem.Soc.2006,128,12634Ortho-ArylationOrtho-ArylationMXR1R2R1R2+M=B,Sn,Si,Mg,ZnX=I,Br,Cl,OTftransition meta
7、l catalystTraddition processC-H bond activation processHYR1R2R1R2+transition metal catalystDGDGY=B,Sn,Si,Mg,Zn I,Br,Cl,OTfOrtho-ArylationOrtho-ArylationRuH2(CO)(PPh3)30.02 mmolOOOBPh+toluene,refluxOOH+1 mmol2 mmol1 mmol1 mmol47%82%40%71%Kakiuchi,F.;et al.J.Am.Chem.Soc.2003,125,1698.J.Am.Chem.Soc.200
8、5,127,5936 Ortho-ArylationOrtho-ArylationRuH2(CO)(PPh3)32 mol%ROOOBPh+pinacolone,refluxOPhO+R=Me Me i-Pr t-Bu1.0 eq2.2 eq2.0 eq1.1 eq17%3%076%39%89%700PhPhKakiuchi,F.;et al.J.Am.Chem.Soc.2005,127,5936HOHORuRuOHRuOOt-BuRuOPhPhOOt-BuBOOOBOOt-BuRuOrtho-ArylationOrtho-ArylationNRHOPdII,CuX2X=Br,ClNRXONR
9、XOPd0baseNRPhO PhB(OH)2+NRPdOviaNRHONRPhOPdPhB(OH)2Wan X.B.,et al.J.Am.Chem.Soc.2006,128,7416.Punna S,et al.Synlett 2004,13,2351.Rodriguez N.;et al.J.Org.Chem.2004,69,8070.Shi Z J.;et al.Angew.Chem.Int.Ed.2007,46,5554Ortho-ArylationOrtho-ArylationNAcArB(OH)2Pd(OAc)2,Cu(OTf)2,Ag2O+toluene,120 C,24 hN
10、Ac20-85%NAcRPhB(OH)2Pd(OAc)2,Cu(OTf)2,Ag2O+toluene,120 C,24 hNRAc41-92%ArPhOrtho-ArylationOrtho-ArylationPdIICLAr2I+PdIVCLAr-Pd(II)CLArKalyani,D.;et al.J.Am.Chem.Soc.2005,127,7330Ortho-ArylationOrtho-ArylationN5 mol%Pd(OAc)2AcOH,110 CPh2IBF4NPh88%N5 mol%Pd(OAc)2AcOH,110 CPh2IBF4NPh91%CHOCHON5 mol%Pd
11、(OAc)2AcOH/Ac2O,110 CPh2IBF4NPh77%CHOOrtho-ArylationOrtho-ArylationNO5 mol%Pd(OAc)2NaHCO3,PhMe,100 CPh2IBF4NOPh84%NOO5 mol%Pd(OAc)2NaHCO3,PhMe,100 CPh2IBF4NoOPh83%NHOCl5 mol%Pd(OAc)2PhH,110 CPh2IBF4NHOClPh67%Ortho-ArylationOrtho-ArylationN5 mol%Pd(OAc)2AcOH,110 CNRI+R=H 85%CF3 87%F 88%Cl 83%CH3 84%O
12、CH3 81%Ortho-ArylationOrtho-ArylationN3-5 mol%Pd(OAc)2AgOAc,AcOH,110-130 CAcINAcNAc73%NAc74%Shabashov,D.;Daugulis,O.Org.Lett.2005,7,3657Ortho-CarbonylationOrtho-CarbonylationNC4H9Ru3(CO)12+CO10 bar150 C,16 hNC4H9ONC4H9O93 :769%Moore,E.J.;et al.J.Am.Chem.Soc.1992,114,5888Ortho-CarbonylationOrtho-Carb
13、onylationHNt-BuRu3(CO)12toluene160 C,12 hCO,CH2=CH2silica gel25 C,1 dayO82%HNt-BuOOHNt-BuFukuyama,T.;et al.J.Org.Chem.1997,62,5647Ortho-SilylationOrtho-SilylationNO+Ru3(CO)12toluene,refluxNOSiEt3HSiEt393%+HSiEt3NH2NH2SiEt3Ru3(CO)12norbornenetoluene,reflux58%Kakiuchi,F.;et al.Chem.Lett.2001,422.Chem.
14、Lett.2002,396OPrPr6 mol%RuH2(CO)(PPh3)3+toluene,135 COPrPr72%,E/Z=16/1Ot-BuMeO1 mol%Pd(OAc)2TFA/CH2Cl2/rtOt-BuOMe90%Kakiuchi,F.;et al.Chem.Lett.1995,681Jia,C.;et al.Science 2000,287,1992NNMeHRO5 mol%MnBr(CO)5toluene115 C,24 h+NNMeROSiEt3HSiEt3R=p-(MeO)C6H4,p-(CF3)C6H4 o-MeC6H4,n-C8H17OS50-89%Kuninob
15、u Y.;et al.Angew.Chem.Int.Ed.2007,46,6518Conclusion and OutlookConclusion and Outlook Outstanding results have been obtained in selectivity and atom economy.These development will help both synthetic and material chemist a great deal Development of milder,lower temperature reaction conditions Fine-tuning of catalyst systems to allow for the industrial use
