第六章氧化反應(yīng)Chapter6-OxidationReactionOxidatingReagent1.OxidationofAlkaneSelectiveoxidationofsaturatedalkaneisverydifficult!!!1.OxidationofAlkaneReactivity:Primary>Secondary>TertiaryBenzylicOxidationCerium(IV)ammoniumnitrate（CAN）Oxidationtoalcohol/esterBenzylicOxidationOxidationtoaldehydeBenzylicOxidationEtard

ComplexEtardComplex:Chromylchloride/alkane2:1OxidationtoketoneOxidationofKetoneOxidationofKetoneOxidationofKetoneOxidationofAllylicCarbonRileyOxidationRileyOxidationMechanismRileyOxidationApplicationsMehta,G.,Shinde,H.M.TetrahedronLett.2003,44,7049-7053.Fürstner,A.,Gastner,T.Org.Lett.2000,2,2467-2470.AllylicOxidationCollinsReagentDoublebondshiftAllylicOxidationVO(OR)Cl2OxidationofAlcohol1.OxidationsofPrimaryandSecondaryAlcoholsIntermolecularIntramolecularOxidationofAlcoholOxidationofAlcoholFormationofcarbonylcompoundsJonesoxidation:Cheap,easytocarryoutsuitableforrobustsubstratesonabigscale.Neithersuitableforveryacidsensitivesubstrates,norforthepreparationofmanyaldehydes.Collinsoxidation:Cheap,butunderanhydrousconditions.Produceverygoodyieldsofaldehydesandketonesinuncomplicatedsubstrates.PDCandPCCaremoreexpensivereagentsthatnormallyguaranteethebestresultsindifficultcases.OxidationofAlcohol-JonesJonesOxidationJonesOxidationWaizumi,N.,Itoh,T.,Fukuyama,T.J.Am.Chem.Soc.2000,122,7825-7826.Crimmins,M.T.,Jung,D.K.,Gray,J.L.J.Am.Chem.Soc.1993,115,3146-3155.OxidationwithMnOxidationwithAg/PbOxidationwithDMSODMSO-DCC(Pfitznor-Moffatt)DCCisthemostwidelyusedactivatingagentthatneedstobeappliedinexcess(usually3equivalentsormore)theoxidationonlyworkswithcatalyststhatareonlymoderatelyacidiccompoundssuchasortho-phosphoricacid(H3PO4),dichloroaceticacidandthepyridiniumsaltsofstrongacidsPfitznor-MoffattOxidationPfitznor-MoffattOxidationSmith,A.B.,III,etal.J.Am.Chem.Soc.1992,114,1438-1449.Ichikawa,S.,etal.J.Am.Chem.Soc.1999,121,10270-10280.Albright-GoldmanOxidationSuitableforoxidationofhinderedalcoholSwernOxidationSwernOxidationHillier,M.C.etal.J.Am.Chem.Soc.1999,121,866-867.Cha,J.K.etal.J.Am.Chem.Soc.2003,125,5415-5421.Parikh–Doering(SulfurTrioxide-MediatedMoffattOxidation)Corey-KimOxidation

Corey-KimOxidation

Kuwajima,I.etal.J.Am.Chem.Soc.2003,125,1498-1500.Zubieta,J.etal.J.Org.Chem.1988,53,3439-3450.HypervalentIodine-Dess-MartinOxidationHypervalentIodine-Dess-MartinOxidationNicolaou,K.C.etal.Org.Lett.1999,1,63-66.IBX(o-iodoxybenzoicacid)LeyOxidationTetrapropylammoniumperruthenate(TPAP)LeyOxidationKeck,G.E.,Knutson,C.E.,Wiles,S.A.Org.Lett.2001,3,707-710.Hu,T.,Panek,J.S.J.Org.Chem.1999,64,3000-3001.OppenauerOxidationOppenauerOxidationSternbach,D.D.,Ensinger,C.L.J.Org.Chem.1990,55,2725-2736.Kocovsky,P.,Baines,R.S.TetrahedronLett.1993,34,6139-6140.AlcoholOxidationtoCarboxylicAcidOxidationofDiolCriegeeOxidationCriegeeOxidationMoricz,A.,Gassman,E.,Bienz,S.,Hesse,M.Helv.Chim.Acta1995,78,663-669.Biju,P.J.,Rao,G.S.R.S.TetrahedronLett.1999,40,9379-9382.OxidationofDiolOxidationofAldehyde/KetoneDakinOxidationDakinOxidationLyttle,M.H.,Carter,T.G.,Cook,R.M.Org.ProcessRes.Dev.2001,5,45-49.OxidationofOlefinOxidationofOlefinOxidationofOlefinPrévostReaction.PrévostReaction.SharplessAsymmetricEpoxidationSharplessAsymmetricEpoxidationHoye,T.R.,Ye,Z.J.Am.Chem.Soc.1996,118,1801-1802.Paterson,I.,DeSavi,C.,Tudge,M.Org.Lett.2001,3,3149-3152.ShiAsymmetricEpoxidationShiAsymmetricEpoxidationHoard,D.W.,etal.Org.Lett.2002,4,1813-1815.Jacobsen-KatsukiEpoxidationJacobsen-KatsukiEpoxidationLynch,J.E.,Choi,W.B.,Churchill,H.R.O.,Volante,R.P.,Reamer,R.A.,Ball,R.G.J.Org.Chem.1997,62,9223-9228.Boger,D.L.,McKie,J.A.,Boyce,C.W.Synlett1997,515-517.SharplessAsymmetricAminohydroxylationSharplessAsymmetricAminohydroxylationDihydroxylationArmstrong,A.,etal.J.Org.Chem.2000,65,7020-7032.Cao,B.,Park,H.,Joullie,M.M.J.Am.Chem.Soc.2002,124,520-521.SharplessAsymmetricDihydroxylationSharplessAsymmetricDihydroxylationOxidationofOlefinLemieux

reagent（NaIO4:KMnO4=6:1）:WackerOxidationWackerOxidationO'Connor,P.D.,Mander,L.N.,McLachlan,M.M.W.Org.Lett.2004,6,703-706.Oxidation

ofAromaticsFremySalt:·ON(SO3K

orNa)2OxidationofAromaticsDehydrogenationDehydrogenationDehydrogenationOxidationofAmineOxidationofAmineKornblumOxidationKornblumOxidationFischer,B.,Kabha,E.,Gendron,F.-P.,Beaudoin,A.R.