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

丁新騰,林子森譯2、《有機合成》斯圖爾特.沃倫著(英)

丁新騰譯3、《基礎有機化學》邢其毅主編4、《新編有機合成化學》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目標分子，目標化合物，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）是一個成熟反應的逆過程。

2）原料易得。切斷點選擇：官能團，如雜原子、羰基、羥基、雙鍵、苯環合成子（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

官能團互換

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

Howwedo?負離子等價物有了兩個好的切斷標準：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，實際是FGI遇到上述結構，FGI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上脂肪側鏈切斷---第三種主要切斷5ControllingProtection!真麻煩！6DisconnectionofSimpleketoneandAcid7LongChainAlkaneHydrogenationisoneofmaymethod交叉點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B)1,2-Diol

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

Comprehensive