ADVANCEDORGANICCHEMISTRYPartIIShanxiNormalUniversity2014CHAPTER6AdditiontoCarbon–CarbonMultipleBondsMECHANISMS

1.1ElectrophilicAddition1.2NucleophilicAddition1.3Free-RadicalAddition1.4CyclicMechanisms1.5AdditiontoConjugatedSystemsORIENTATIONANDREACTIVITY

2.1Orientation2.2StereochemicalOrientation2.3AdditiontoCyclopropaneRings3.REACTIONS

MECHANISMS1.1ElectrophilicAddition-980C,H2CCl2,synaddition00C,Et2O,antiaddition1.2NucleophilicAdditionC=C-ZZ=CHO,COR

,COOR,CONH2,CN,NO2,SOR,SO2R,andsoon1.3Free-RadicalAdditionor1.4CyclicMechanisms1.5AdditiontoConjugatedSystemsTABLE6.1.RelativeReactivityofSomeAlkenesTowardBromineinAceticAcidat240CTABLE6.2.RelativeReactivityofSomeAlkenesTowardBromineinMethanolORIENTATIONANDREACTIVITY

ElectrophilicadditionNucleophilicadditionZ=NO2,COAr,CHO,COR,SO2Ar,CN,COOR,SOAr,CONH2,CONHR.OrientationStereochemicalOrientationAdditiontoCyclopropaneRings3.REACTIONSISOMERIZATIONOFDOUBLEANDTRIPLEBONDS6-1IsomerizationREACTIONSINWHICHHYDROGENADDSTOONESIDEA.HalogenontheOtherSide6-2AdditionofHydrogenHalidesB.OxygenontheOtherSide6-3HydrationofDoublebonds6-4HydrationofTripleBonds6-5AdditionofAlcoholsandPhenols6-6AdditionofCarboxylicAcidstoFormEstersC.SulfurontheOtherSide6-7AdditionofH2SandThiolsD.NitrogenorPhosphorusontheOtherSide6-8AdditionofAmmoniaandAmines,Phosphines,andRelatedCompoundsPd,Mo,Rh,La6-9AdditionofAmides6-10AdditionofHydrazoicAcidTiCl4E.HydrogenonBothSides6-11HydrogenationofDoubleandTripleBondscatalystsinsolubleinthereactionmedium(heterogeneouscatalysts).AmongthemosteffectiveareRaneynickel,palladium-on-charcoal(perhapsthemostcommon),NaBH4-reducednickel(alsocallednickelboride),platinummetaloritsoxide,rhodium,ruthenium,andzincoxide.(2)Catalystssolubleinthereactionmedium(homogeneouscatalysts).Animportantexampleischlorotris(triphenylphosphine)rhodium,RhCl(Ph3P)3,(Wilkinson’scatalyst)whichcatalyzesthehydrogenationofmanyalkenylcompoundswithoutdisturbingsuchgroupsasCOOR,NO2,CN,orCORpresentinthesamemolecule.AparticularlygoodcatalystforthispurposeistheLindlarcatalyst(Pd-CaCO3-PbO),Analternativecatalystusedforselectivehydrogenationtocisalkenesispalladiumonbariumsulfate(BaSO4)catalyst,poisonedwithquinoline.Palladiumoncalciumcarbonateinpolyethyleneglycol(PEG)hasalsobeeusedasarecyclablecatalystsystem.6-12OtherReductionsofDoubleandTripleBondsNH2NH2,NH2OH6-13HydrogenationofAromaticRings6-14ReductionOfTheDoubleorTripleBondsConjugatedtoCarbonyls,Cyano,andsoon.6-6ReductiveCleavageofCyclopropanesF.AMetalontheOtherSide6-16HydroborationTHF-BH3,R3N-BH3BH2Cl-SMe26-17OtherHydrometalationG.CarbonorSiliconontheOtherSide6-18AdditionofAlkanes6-19AdditionofSilanes6-20AdditionofAlkenesand/orAlkynestoAlkenesand/orAlkynesCouplingreactionscanoccurusingcatalystsystemsconsistingofnickelcomplexesandalkylaluminumcompounds(knownasZieglercatalysts),rhodiumCatalysts,andothertransition-metalcatalysts,includingiron.Nazarovcyclization.6-21AdditionofOrganometallicstoDoubleandTripleBondsNotConjugatedtoCarbonyls6-22TheAdditionofTwoAlkylGroupstoanAlkyne(PhMe2Si)2Cu(CN)LiGrignardreagents(benzylic,allylic)6-23TheEneReaction6-24TheMichaelReaction6-251,4-AdditionofOrganometallicCompoundstoActivatedDoubleBonds6-26TheSakuraiReaction6-27ConjugateAdditionofBoranestoActivatedDoubleBonds6-28RadicalAdditiontoActivatedDoubleBonds6-29RadicalAdditiontoUnactivatedDoubleBond6-30RadicalCyclization6-32AcylationofActivatedDoubleBondsandofTripleBonds6-33AdditionofAlcohols,Amines,CarboxylicEsters,Aldehydes,andsoon.6-34AdditionofAldehydesRhodiumcompoundsorYb(OTf)36-35Hydrocarboxylation100–350oCand500–1000atm6-36Carbonylation,AlkoxycarbonylationandAminocarbonylationofDoubleandTripleBondsCuCl2andPdCl26-37Hydroformylation6-38AdditionofHCNCuCl,NH4Cl,andHCl；NiorPdcompounds.Et2AlCN,HCNandR3Al6-39HalogenationofDoubleandTripleBondsp-TolIF2/Et3N·5HFamixtureofPbO2andSF4Me3SiClMnO2,

NaClO2/Mn(acac)2/moistAl2O3,BnNEt3MnO4/Me3SiCl,

andKMnO4-oxalylchloride.C5H5NHBr3(decyl)Me3NMnO4andMe3SiBrCuBr2orCuCl2BrCl>ICl>Br2>IBr>I26-40AdditionofHypohalousAcidsandHypohalites6-41HalolactonizationandHalolactamization6-42AdditionofSulfurCompounds6-43AdditionofHalogenandanAminoGroup6-44AdditionofNOXandNO2X6-45AdditionofXN36-46AdditionofAlkylHalidesCCl4,BrCCl3,ICF36-47AdditionofAcylHalides6-48Hydroxylation6-49DihydroxylationofAromaticRings6-50Epoxidation6-51Hydroxysulfenylation6-