有機(jī)合成(部編)課件

有機(jī)合成路線及分子設(shè)計(jì)RoutesandMolecularDesigninOrganicSynthesis參考書1、《有機(jī)合成設(shè)計(jì)》斯圖爾特.沃倫著(英)

丁新騰,林子森譯2、《有機(jī)合成》斯圖爾特.沃倫著(英)

丁新騰譯3、《基礎(chǔ)有機(jī)化學(xué)》邢其毅主編4、《新編有機(jī)合成化學(xué)》黃憲、王彥廣、陳振初編著----PreparationofAlkane----1.HydrogenationofAlkenes2.ReductionofAlkylHalides3.CouplingofAlkylHalideswithOrganometalicCompounds----PreparationofAlkane--------PreparationofAlkene----1.DehydrohalogenationofAlkylHalide2.DehydrationofAlcohols3.DehalogenationofVicinalDihalides4.ReductionofAlkynes----PreparationofAlkene--------PreparationofAlcohol----1.Oxymercuration-Demercuration2.Hydroboration-Oxidation3.GrignardSynthesis4.HydrolysisofAlkylHalides5.HydroxylationofAlkenes----PreparationofAlcohol--------PreparationofHalide----1.FromAlcohols2.HalogenationofCertainhydrocarbons3.AdditionofHydrogenHalidetoAlkenes4.AdditionofHalogentoAlkenesandAlkynes5.HalideExchange----PreparationofHalide--------PreparationofEther----1.WilliamsonSynthesis2.Alkoxymercuration-Demercuration----PreparationofEther--------PreparationofAlkylbenzene----1.Friedel-CraftsAlkylation2.ConversionofSideChain----PreparationofAlkylbenzene--------PreparationofPhenol----1.HydrolysisofDiazoniumSalts2.AlkliFusionofSulfonates----PreparationofPhenol--------PreparationofAmine----1.ReductionofNitroCompounds2.ReactionofHalideswithammoniaorAmines3.ReductiveAmination4.ReductionofNitriles5.HofmannDegradationofAmides----PreparationofAmine--------ReactionofDiazonium----1.ReplacementofNitrogen2.Coupling----ReactionofDiazonium--------PreparationofAldehyde&Ketone----1.OxidationofPrimaryAlcohols2.OxidationofMethylbenzene3.ReductionofAcidchlorideAldehydeKetone1.OxidationofSecondaryAlcohols2.Friedel-CraftsAcylation----PreparationofAldehyde&Ketone--------ReactionsofAldehyde&Ketone----1.Oxidation2.Reduction3.AdditionofCyanide4.AdditionDerivativesofammonia5.AdditionofAlcohols6.CannizzaroReaction7.AdditionofGrignardReagent----ReactionsofAldehyde&Ketone--------ReactionofCarbanion----1.Halogenationofketones2.Nucleophilic

AdditontoCarbonylCompounds3.Nucleophilic

AcylSubstitution----ReactionofCarbanion--------SubstitutiononAromaticRing----1.Nitration2.Sulfonation3.Halogenation4.Friedel-CraftsAlkylation5.Friedel-CraftsAcylation6.Protonation----SubstitutiononAromaticRing--------PreparationofAcid----1.OxidationofPrimaryAlcohols2.OxidationofAlkylbenzene3.CarbonationofGrignardReagent4.HydrolysisofNitriles----PreparationofAcid----BasicTermsAimAimedTarget//CompoundMolecule目標(biāo)分子，目標(biāo)化合物，靶分子切斷-合成子

Disconnection-Synthon切斷：將分子中的一個鍵斷開。符號：條件：1）是一個成熟反應(yīng)的逆過程。

2）原料易得。切斷點(diǎn)選擇：官能團(tuán)，如雜原子、羰基、羥基、雙鍵、苯環(huán)合成子（synthon）：切斷時得到的概念性碎片合成等價物：能起合成子作用的試劑。FGI:FunctionalGroupInterconversion

官能團(tuán)互換

FGI：把一個官能團(tuán)轉(zhuǎn)換成另一種官能團(tuán)。目的：使一種切斷成為可能。符號：切斷的選擇DisconnectionofmonoFunctionalGroup1.SimpleAlcohol選擇最穩(wěn)定的負(fù)離子處切斷通常情況是沒有一個取代基能給出穩(wěn)定負(fù)離子

Howwedo?負(fù)離子等價物有了兩個好的切斷標(biāo)準(zhǔn)：1）合理。2）簡單帶有兩個相同取代基的叔醇=酯+2GrignardNaBH4

只能還原醛，酮。不能還原酯LiAlH4

能還原所有羰基化合物2Derivativesofalcohol涉及H-還原時，實(shí)際是FGI遇到上述結(jié)構(gòu)，F(xiàn)GI到醇是一種好的思路Homework3DisconnectionofsimplealkeneAdditionofH2O切斷：1）合理。2）簡單。3）原料易得4DisconnectionofAromaticKetone將醇切斷成羰基化合物和Grignard試劑----第一種主要切割將烯鍵切斷成羰基化合物和Wittig試劑----第二種主要切斷將芳香環(huán)上脂肪側(cè)鏈切斷---第三種主要切斷5ControllingProtection!真麻煩！6DisconnectionofSimpleketoneandAcid7LongChainAlkaneHydrogenationisoneofmaymethod交叉點(diǎn)WorkChapter4:DisconnectionofBifunctionalGroups1).1,3-oxidizedskeletonA)3-hydroxycarbonylsB)2,3-UnsaturatedcarbonylcompoundC)1,3-DicarbonylcompoundStableanionwork2)1,5-DicarbonylcompoundMichaeladditionisveryimportantinsomelongsyntheticprocesses.Mannichreaction&2,3-ketenoneWorkChapter5:DisconnectionofSpecialBifunctionalGroup1)1,2-oxidizedskeletonA)2-hydroxycarbonylBenzoinreaction苯偶姻反應(yīng)B)1,2-Diol

PinacolRearrangementWork!2)1,4-OxidizedSkeletonA)1,4-DicarbonylCompoundB)4-HydroxyCarbonylCompoundWork3)1,6-DicarbonylCompoundWork

Comprehensive