TransitionMetal-CatalyzedC-HBondActivationofAromaticCompounds：Chelation-AssistedOrtho-FunctionalizationOutlineIntroductionCatalyticOrtho-FunctionalizationConclusionandOutlookIntroductionDGHtransitionmetalcatalystDGFGDG=directinggroupFG=functionalgroupRRIntroductionOH+C2H4[Ru]OHOH+THF,177°C,KOPh75%13%RuPP(OPPh)3PP(OPh)3OPhPOO[Ru]=PhPOOPPhOPPhLewis,L.N.;Smith,J.F,J.Am.Chem.Soc.1986,108,2728IntroductionR1OR2+Y2mol%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%Murai,S.;etal.Nature1993,366,529IntroductionO[Ru]O[Ru]O[Ru]HO[Ru]SiMe3SiMe3OSiMe3AdvantagesHighselectivityAtomeconomyCleanandeconomicalprocessCatalyticOrtho-FunctionalizationOrtho-AlkylationOrtho-ArylationOrtho-CarbonylationOthersOrtho-AlkylationR1NPh+R3R2(1)2mol%Rh(PPh3)3Cltoluene,150°C,2h(2)H3O+R1OR2R3R1=Me,Et,n-PentR2=CF3,H,CH3OR3=alkyl,aryl,silylupto97%Jun,C.H.Angew.Chem.Int.Ed.2000,39,3440Ortho-AlkylationHNPhOMeOO(1)10mol%[Rh(coe)2Cl]220mol%FcPCy2toluene,150°C,2h(2)H3O+HOMeOOOFcPCy2=FePCy2HOMeOOOMeOOONH2¡¤HCl65%Ahrendt,K.A.;etal.Org.Lett.2003,5,1301Ortho-AlkylationHNBn(1)5mol%[Rh(coe)2Cl]215mol%ligand,tolueneHNBnOPN(CHCH3Ph)2ligand94%95%eeHNBnPh96%90%eeHNBnN90%70%eeHNBnO95%96%eeOThalji,R.K.;etal.J.Am.Chem.Soc.2004,126,7192Ortho-AlkylationNXHRB(OH)2/Ag2OorAg2CO3ormethylboroxine/Cu(OAc)2catPd(OAc)2benzoquinone,airNXRR=Me,Et,n-Bu,n-Hex,Ph(CH2)2,cyclopropylNOBOBOBMeMeMePdIINOBOBOBMeMeMePdIIintramoleculartransmatalationNMeChenX.;etal.J.Am.Chem.Soc.2006,128,12634Ortho-ArylationMXR1R2R1R2+M=B,Sn,Si,Mg,ZnX=I,Br,Cl,OTftransitionmetalcatalystTradditionprocessC-HbondactivationprocessHYR1R2R1R2+transitionmetalcatalystDGDGY=B,Sn,Si,Mg,ZnI,Br,Cl,OTfOrtho-ArylationRuH2(CO)(PPh3)30.02mmolOOOBPh+toluene,refluxOOH+1mmol2mmol1mmol1mmol47%82%40%71%Kakiuchi,F.;etal.J.Am.Chem.Soc.2003,125,1698.J.Am.Chem.Soc.2005,127,5936Ortho-ArylationRuH2(CO)(PPh3)32mol%ROOOBPh+pinacolone,refluxOPhO+R=MeMei-Prt-Bu1.0eq2.2eq2.0eq1.1eq17%3%076%39%89%700PhPhKakiuchi,F.;etal.J.Am.Chem.Soc.2005,127,5936HOHORuRuOHRuOOt-BuRuOPhPhOOt-BuBOOOBOOt-BuRuOrtho-ArylationNRHOPdII,CuX2X=Br,ClNRXONRXOPd0baseNRPhOPhB(OH)2+NRPdOviaNRHONRPhOPdPhB(OH)2WanX.B.,etal.J.Am.Chem.Soc.2006,128,7416.PunnaS,etal.Synlett2004,13,2351.RodriguezN.;etal.J.Org.Chem.2004,69,8070.ShiZJ.;etal.Angew.Chem.Int.Ed.2007,46,5554Ortho-ArylationNAcArB(OH)2Pd(OAc)2,Cu(OTf)2,Ag2O+toluene,120°C,24hNAc20-85%NAcRPhB(OH)2Pd(OAc)2,Cu(OTf)2,Ag2O+toluene,120°C,24hNRAc41-92%ArPhOrtho-ArylationPdIICL[Ar2I]+PdIVCLAr-Pd(II)CLArKalyani,D.;etal.J.Am.Chem.Soc.2005,127,7330Ortho-ArylationN5mol%Pd(OAc)2AcOH,110°C[Ph2I]BF4NPh88%N5mol%Pd(OAc)2AcOH,110°C[Ph2I]BF4NPh91%CHOCHON5mol%Pd(OAc)2AcOH/Ac2O,110°C[Ph2I]BF4NPh77%CHOOrtho-ArylationNO5mol%Pd(OAc)2NaHCO3,PhMe,100°C[Ph2I]BF4NOPh84%NOO5mol%Pd(OAc)2NaHCO3,PhMe,100°C[Ph2I]BF4NoOPh83%NHOCl5mol%Pd(OAc)2PhH,110°C[Ph2I]BF4NHOClPh67%Ortho-ArylationN5mol%Pd(OAc)2AcOH,110°CNRI+R=H85%CF387%F88%Cl83%CH384%OCH381%Ortho-ArylationN3-5mol%Pd(OAc)2AgOAc,AcOH,110-130°CAcINAcNAc73%NAc74%Shabashov,D.;Daugulis,O.Org.Lett.2005,7,3657Ortho-CarbonylationNC4H9Ru3(CO)12+++CO10bar150°C,16hNC4H9ONC4H9O93:769%Moore,E.J.;etal.J.Am.Chem.Soc.1992,114,5888Ortho-CarbonylationHNt-BuRu3(CO)12toluene160°C,12hCO,CH2=CH2silicagel25°C,1dayO82%HNt-BuOOHNt-BuFukuyama,T.;etal.J.Org.Chem.1997,62,5647Ortho-SilylationNO++Ru3(CO)12toluene,refluxNOSiEt3HSiEt393%+HSiEt3NH2NH2SiEt3Ru3(CO)12norbornenetoluene,reflux58%Kakiuchi,F.;etal.Chem.Lett.2001,422.Chem.Lett.2002,396OPrPr6mol%RuH2(CO)(PPh3)3+toluene,135°COPrPr72%,E/Z=16/1Ot-BuMeO1mol%Pd(OAc)2TFA/CH2Cl2/rtOt-BuOMe90%Kakiuchi,F.;etal.Chem.Lett.1995,681Jia,C.;etal.Science2000,287,1992NNMeHRO5mol%MnBr(CO)5toluene115°C,24h++NNMeROSiEt3HSiEt3R=p-(MeO)C6H4,p-(CF3)C6H4o-MeC6H4,n-C8H17OS50-89%KuninobuY.;etal.Angew.Chem.Int.Ed.2007,46,6518ConclusionandOutlookOutstandingresultshavebeenobtainedinselectivityandatomeconomy.ThesedevelopmentwillhelpbothsyntheticandmaterialchemistagreatdealDevelopmentofmilder,lowertemperaturereactionconditionsFine-tuningofcatalystsystemstoallowfortheindustrialuse
