硝酰基自由基调节的乙醇氧分子氧化课件

NitroxylRadical-mediatedOxidationofAlcoholswithMolecularOxygenContentsIntroduction(Researchbackground)ThedifferentnitroxylradicalsTEMPO-mediatedalcoholsoxidationPINO(like)-mediatedalcoholsoxidationConclusionsTEMPOPINOIntroductionReactionequation:Aldehydes,ketonesandacidsarecrucialindustrialproducts.Theworld-wideannualproductionofcarbonylcompoundsisover10,000,000tonnesandmanyofthesecompoundsareproducedfromtheoxidationofalcohols.Direction:green,environment-friendlycatalyticprocesses.Catalyticsystem:transitionmetal,oxidaseenzyme,nitroxylradicalThedifferentnitroxylradicalsSheldon,R.A.;Arends,I.W.C.E.J.Mol.Catal.A:Chemical,2006,251,200–214TEMPO-mediatedalcoholoxidationRu/TEMPOcatalyticsystemCu/TEMPOcatalyticsystemLaccase/TEMPOcatalyticsystemFe-NaNO2/TEMPOcatalyticsystemTransitionmetal-freecatalyticsystemE0=0.53VRu/TEMPOcatalyticsystemDijksman,A.;Marino-Gonzalez,A.;MairataiPayeras,A.etc.J.Am.Chem.Soc.2001,123,6826–6833EntrySubstrateS/CratioTime(h)Conv.(%)TON1Octan-2-ol100798982Octan-1-ol507854331-phenylethanol1004>991004cyclooctanol100792925Benzylalcohol2002.5>992006Benzylalcohol/1-phenylethanol200390/5180/1015mmolofsubstrate,RuCl2(PPh3)3/TEMPOratioof1:3,30mLchlorobenzeneTable4oxidationofalcoholsbyRu/TEMPOsystemRu/TEMPOcatalyzedoxidationmechanismShedon,R.A.;Arends,I.W.C.E.;Brink,G.-J.T.;etc.,AccountsofChemicalResearch,2002,35,9,774-781Sheldon,R.A.;Arends,I.W.C.E.;Adv.Synth.Catal.2004,346,1051–1071Scheme3Ru-catalyzedoxidationofalcoholswithmolecularoxygenCu(I)/TEMPOsystemforalcoholsoxidationentryalcoholproducttime(h)conversionyield115987221697903159796436967558398736169890Ansari,I.A.;Gree,R.Org.Lett.2002,4,1507–1509Benzylalcohol(108mg,1.0mmol)1.5mL[bmim][PF6];1atmO2

Table1oxidationofalcoholbyCu(I)/TEMPOsystemSchultz,M.J.andSigman,M.S.Tetrahedron,2006,62,8227–8241Oxidationofaliphaticalcoholswerenothighefficient.Cu(Ⅱ)/TEMPOcatalyticsystemVelusamy,S.;Srinivasan,A.andPunniyamurthy,T.TetrahedronLetters,2006,47,923–926EntrySubstrateProductTime(h)Yield(%)1109721498399842190522756122Alcohol(5mmol)intoluene(10mL)underatmosphericoxygenTable2oxidationofalcoholsbyCu(Ⅱ)/TEMPOsystemCu/TEMPOcatalyzedoxidationmechanismGamez,P.;Arends,I.W.C.E.;Sheldon,R.A.;Reedijk,J.Adv.Synth.Catal.2004,346,805–811Scheme2Cu-TEMPOcatalyzedaerobicalcoholsoxidationRecentdevelopmentofCu-catalyzedsystemJiang,N.;Ragauskas,A.J.Org.Lett.2005,7,3689–3692Acetamido-TEMPOEntryAlcoholProductTime(h)ConversionYield12100982299933298934241911529871629992Alcohol(2mmol),under1atmoxygenJiang,N.andRagauskas,A.J.,J.Org.Chem.2006,71,7078-7090Table3oxidationofalcoholsbyCu(ClO4)2/TMDP/DABCD/acetamido-TEMPOsystemDACBO:1,4-diazabicyclo[2.2.2]octaneLaccase/TEMPOcatalyticsystemEntrySubstrateProductYield(%)1benzylalcoholbenzaldehyde9223,4-dimethoxybenzylalcohol3,4-dimethoxybenzaldehyde993cinnamylalcoholcinnamaldehyde9445-hexen-1-ol5-hexen-1-al195cyclohexanolcyclohexanone35Fabbrini,M.;Galli,C.andGentili,P.etc.TetrahedronLetters2001,

42,7551–7553Reactionconditions:subst.:20mM,TEMPO:6mM,3U/mLoflaccase,3mLwater(pH4.5);time:24h;r.t.Table6OxidationofAlcoholsbyLaccase-TEMPOcatalyticsystemScheme4themechanismofalcoholsoxidationbyLaccase/TEMPOsystemItmainlycatalyzedoxidationofacloholswithrichelectrons.RecentdevelopmentofLaccase-

catalyzedsystemEntryMediatorAcetatebufferWater/toluene1TEMPO66.827.624-hydroxy-TEMPO76.860.734-acetylamino-TEMPO78.581.7Arends,I.W.C.E.;Li,Y.;Ausan,R.andSheldon,R.A.Tetrahedron2006,62,6659–6665[Sub]0:125mM,Lac:5.9U/ml,[Med]:19mM,rt,1atmO24-hydroxy-TEMPO4-acetylamino-TEMPOTable7oxidationofbenzylalcoholbyLaccase/TEMPO-likesystemFe-NaNO2/TEMPOsystemEntrysubstrateTime(h)Conversion(%)18>9928>99312>99412>9958>99Wang,N.;Liu,R.;Chen,J.;Liang,X.Chem.Commun.2005,5322–5324substrate:10mmol,PhCF3:10mLTable5oxidationofalcoholsbyFe-NaNO2/TEMPOsystemTransitionmetal-freeTEMPO-mediatedcatalyticsystemEntrySubstrateProductTimeConv.(%)Select.(%)Yield(%)111001009521.5100999833-C8H17OH3-Octanone499.199.3884410099.4895594.4100-Liu,R.;Liang,X.;Dong,C.andHu,X.J.Am.Chem.Soc.2004,126,4112-4113Table8oxidationofalcoholsbyTEMPO/NaNO2/Br2systemReactionconditions:substrate(10mmol),TEMPO(0.1mmol),Br2(0.4mmol),CH2Cl2(10mL),80℃,NaNO2(0.4mmol),0.4MPaairpressureTheoxidationmechanismby

TEMPO-Br2-NaNO2systemThereinto,theuseofNOtoactivatemolecularoxygenplaysacrucialroleintheTEMPO/Br2/NaNO2catalyticoxidationcycle.Scheme5oxidationofalcoholsbyTEMPO-Br2-NaNO2systemSupported-TEMPO-mediatedcatalyticsystemDijksman,A.;Arends,I.W.C.E.;Sheldon,R.A.Synlett2001,102–104.Oxidationresultsbysupported-TEMPOEntryCatalystS/CTime(h)Conv.(%)TOF1PIPO10020452.32PIPO101.5966.43MCM-41TEMPO10024200.94SiO2TEMPO1002040.210mmolbenzylalcohol,CuCl:nitroxyl=1:1,25mlDMF,25℃,oxygenatmosphereTable9OxidationofbenzylalcoholbydifferentsupportedTEMPORecentdevelopmentofmediatorsfor

alcoholsoxidationQian,W.;Jin,E.;.Bao,W.andZhang,Y.Tetrahedron2006,62,556–562Shibuya,M.;Tomizawa,M.;Suzuki,I.andIwabuchi,Y.J.Am.Chem.Soc.2006,128,8412-8413PINO-mediatedalcoholsoxidationHeteropolyacid/NHPIcatalyticsystemCo/NHPIcatalyticsystemV/NHPIcatalyticsystemNHPIHeteropolyacid/NHPIcatalyticsystementrySubstrateTime(h)Yield(%)15(41)

(23)25(56)Ishii,Y.;Nakayama,K.;Takeno,M.;Sakaguchi,S.;Iwahama,T.;Nishiyama,Y.J.Org.Chem.1995,60,3934-3935Substrate(2mmol)wasreactedinthepresenceofNHPI(10mol%)inPhCN(5

mL),100℃,underadioxygenatmosphereTable10oxidationofalcoholsbyheteropolyacid/NHPIsystem

Iwahama,T.;Yoshino,Y.;Keitoku,T.;Sakaguchi,S.;Ishii,Y.J.Org.Chem.2000,65,6502–6507Co/NHPIcatalyticsystementrySubstrateTime(h)Yield(%)115982206732075420835207862084Alcohol(3mmol),AcOEt(5mL)Table11oxidationofalcoholsbyCo/NHPIsystemV/NHPIcatalyticsystemP.J.Figiel,J.M.SobczakandJ.J.Ziólkowski,Chem.Commun.,2004,244-245EntryAlcoholCo-catalystConversion(%)Time/hSelectivity(%)1CyclohexanolVO(acac)2+Bu4NCl90.31866.42CyclohexanolVO(acac)2+LiCl81.721003CyclohexanolVO(acac)2Cl89.21860.14CyclohexanolVO(OPr)3+LiCl80.1189.052-PentanolVO(acac)2+LiCl96.420>9961-HexanolVO(acac)2+LiCl1002296.65mmolsubstrate,75℃Table12oxidationofalcoholsbyV/NHPIsystemSINO-mediatedalcoholsoxidationentryalcoholTime(h)Conversion(%)ProductYield(%)159392239694321009849866754100100Baucherel,X.;Gonsalvi,L.;Arends,I.W.C.E.;Ellwood,S.andSheldon,