碳原子周围电子云密度降低即氧化数态值升高反应课件

ConceptofoxidationConceptofoxidationGeneral化数(氧化态，氧化值)升高的反应。Narrow加氧反应和/或脱氢反应。2碳原子上的氢被吸电子基团或原子取 碳原子上的氢被吸电子基团或原子取 RCH3碳碳相联接转变成与吸电子基团或原子相碳碳相联接转变成与吸电子基团或原子相联2O4脱++功能团的氧脱++功能团的氧5PerfectoxidationPerfectoxidationHighMildreactionFriendlyenvironmentConvenientandcheapmaterials6Epoxidation——OxidationofCarbon-CarbonDoubleComprehensiveOrg.Syn.,Vol.1,819;Vol.Epoxidation——OxidationofCarbon-CarbonDoubleComprehensiveOrg.Syn.,Vol.1,819;Vol.7,357,PeracidOOOOCC++RR71.PeracidORORateR=CH3<C61.PeracidORORateR=CH3<C6H5<m-<H<p-<pKaofacid0ThelowerthepKa,thegreaterthe(i.e.,thebettertheleaving82.OOR1CCHORRRROHOORRRRRRRR过氧酸对双键发生亲电进攻，形成环氧化合物92.OOR1CCHORRRROHOORRRRRRRR过氧酸对双键发生亲电进攻，形成环氧化合物93.Stereochemistryofolefinismaintained:Reactionrateisinsensitivetosolventpolarityimplyingconcertedmechanism3.Stereochemistryofolefinismaintained:Reactionrateisinsensitivetosolventpolarityimplyingconcertedmechanismwithoutintermediacyofionicintermediat.LesshinderedfaceofolefinisRRRRRRO+O20min.2524h,25R=R=BrownJ.Am.Chem.Soc.1970,92,4.--Electrophilicreagent:mostnucleophilicC=Creacts>>R>>>4.--Electrophilicreagent:mostnucleophilicC=Creacts>>R>>>>>Om--10oC,cis:transOCHCl,10min.3ConcavefacehinderedtowardperacidattackH OOHHOOm--10oC,cis:transOCHCl,10min.3ConcavefacehinderedtowardperacidattackH OOHHOC6H6-25oC,OHHHHConvexfaceopentoperacid5.EndocyclicRickbornJ.5.EndocyclicRickbornJ.Org.Chem.1965,30,DestabilizingstericinteractionbetweenreagentandaxialMe HHAttackprincipallyfromthisfaceExocyclicHenbest,J.Chem.Soc.,Chem.Commun.,1967,morehinderedExocyclicHenbest,J.Chem.Soc.,Chem.Commun.,1967,morehindered O+ lesshindered lessstable--Solvent CH2Cl2or AllylicAlcoholsHenbestJ.AllylicAlcoholsHenbestJ.Chem.Soc.1957,1958;Proc.Chem.Soc.1963, m- R= 20oC 38%R= 5 86%OO +Bu-Bu-Bu-Prefersequatorialposition,lockoingconformationofsubstrate.OO +Bu-Bu-Bu-Prefersequatorialposition,lockoingconformationofsubstrate. O120 Metal-catalyzedepoxidationsMetal-catalyzedepoxidationsofallylicSharpless，AldrichimicaActa1979,12,AllylicAlcoholsVedejsandAllylicAlcoholsVedejsandDentJ.Am.Chem.Soc.1989,111,AcyclicAllylicAcyclicAllylicHHvs.alkyleclipsinginteractionwithdoublebondhaslittletonoeffectonselectivity.HeclipsinginteractionslightlymoreHHH =VO(acac),t-1R2HHvs.alkyleclipsinginteractionwithdoublebondhaslittletonoeffectonselectivity.HeclipsinginteractionslightlymoreHHH =VO(acac),t-1R2VO(acac)2,t-=HHHH=i-H,HeclipsinginerythroT.s.favoredinthreoT.S.VO(acac)2,t-5HHHErythroslightlyfavoredduetoMe,MegaucheinteractioninthreoT.S.m- R,R=VO(acac)2,t-HHm-5HHHErythroslightlyfavoredduetoMe,MegaucheinteractioninthreoT.S.m- R,R=VO(acac)2,t-HHm-H,BueclipsinginerythroT.s.favoredoverMe,BueclipsinginthreoT.S.=H2R 2HomoallylicAlcohols(高烯丙系HL OOO PhOTBDPSCHHomoallylicAlcohols(高烯丙系HL OOO PhOTBDPSCH2Cl2,H--Alternativechairhastwoaxial--Intermolecularoxygendeliveryoccursthroughmoststablechair-liketransitionstate.OCH2Cl2,25oCH)OAc--H-Eclipsed--EpoxidationOCH2Cl2,25oCH)OAc--H-Eclipsed--Epoxidationfromleasthindered--Notadirected--DiadtereoselectivitystillgoodandthroughH-eclipsedSchreibe,TetrahedronLett.1990,31,Hanessian,J.AmChemSoc,1990,112,OtherDirectedOtherDirected--Studiessuggestaxial–NHCBZdeliverssynepoxidewhileequatorialdoesnot.MohamadiTetrahedronMohamadiTetrahedronLett.1989,30,6.ScopeandO+Olefin6.ScopeandO+OlefingeometryisReactionisdiastereospecific:thestereochemistryofthereactantandproductbearadefiniterelationshiptooneanother.Reactioncanbebufferedtopreventepoxided.Athighertemperatures,afreeradicalscavengermaybeusedtoavoidperaciddecomposition.e.CommonSide1)Baeyer-VilligerReactionsofKetonesd.Athighertemperatures,afreeradicalscavengermaybeusedtoavoidperaciddecomposition.e.CommonSide1)Baeyer-VilligerReactionsofKetones(andOOOO O2)Oxidationof--Nitrogenmustbeprotected(e.g.asamide)oranotherreagent3)2)Oxidationof--Nitrogenmustbeprotected(e.g.asamide)oranotherreagent3)Imine4)Sulfur m- EpoxidationofElectron-Deficient,-unsaturatedesters:canchooseastrongperacidorvigorousreactionconditions.Emmons,J.Am.Chem.Soc.EpoxidationofElectron-Deficient,-unsaturatedesters:canchooseastrongperacidorvigorousreactionconditions.Emmons,J.Am.Chem.Soc.,1955,77,89.CH2Cl2,OCO MacPeek,J.Am.Chem.1959,81,b.,-unsaturatedketone:Baeyer-VilligercompeteswithSolution:differentconditions(reagents)areO Baeyer-Villiger CH2Cl2,AdditionalMethodsforEpoxidationof1.H2O2,OOHH2AdditionalMethodsforEpoxidationof1.H2O2,OOHH2O2,OOO--Thefollowingreactionisdiastereoselective(notO MeHH2O2,H2O2,Thereactionoccursviaareversible--Thefollowingreactionisdiastereoselective(notO MeHH2O2,H2O2,ThereactionoccursviaareversibleOCOH23tBuOOH/TritonBPayneJ.Org.Chem.,1961,26,CoreyJ.Am.Chem.Soc.1988,110,CeggTetrahedron,1988,29,2.--Thisreagentpermitstheuseofneutralreactionconditions2.--Thisreagentpermitstheuseofneutralreactionconditions.Unlikem-CPBA,thereagentbehavesasalargereagentandthusaproachesfromtheequatorialfaceofanexocyclicdouble--Analogous 1980,19,458.H --Analogous 1980,19,458.H smallreagent,buttheCarlson,J.Org.Chem., willincreasewithsizeofthe32,1363.(m-CPBA&Vedejs,J.Am.Chem. 1989,111,6861.(m- largereagent,buttheinteractionnotvarywithsize,predominatelyequatorialattack.3.Sulfur--Thisistheresultofkineticcontrol:reactiongivesthethermodynamicallylessstableepoxideproduct.HH)(Bu-Bu-Equatorial1,2-interactionOBu-Bu-O-)3.Sulfur--Thisistheresultofkineticcontrol:reactiongivesthethermodynamicallylessstableepoxideproduct.HH)(Bu-Bu-Equatorial1,2-interactionOBu-Bu-O-)( HAxial1,3-interactionfavoredoverCorey,Chaykovsky,J.Am.Chem.Soc.,1965,87,Bu-Bu-O+OO0DimethoxoCorey,Chaykovsky,J.Am.Chem.Soc.,1965,87,Bu-Bu-O+OO0DimethoxosulfoniumSmallreagentthatprefersaxialInitialreactionisreversibleandisnotcapableofgeneratingtheaxialdeliveryproductbecauseofthedestabilizing1,3-interactionsinthetransitionstaterequiredforepoxideclosure. 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