有机合成(部编)课件

有机合成路线及分子设计RoutesandMolecularDesigninOrganicSynthesis参考书1、《有机合成设计》斯图尔特.沃伦著(英)

丁新腾,林子森译2、《有机合成》斯图尔特.沃伦著(英)

丁新腾译3、《基础有机化学》邢其毅主编4、《新编有机合成化学》黄宪、王彦广、陈振初编著----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目标分子，目标化合物，靶分子切断-合成子

Disconnection-Synthon切断：将分子中的一个键断开。符号：条件：1）是一个成熟反应的逆过程。

2）原料易得。切断点选择：官能团，如杂原子、羰基、羟基、双键、苯环合成子（synthon）：切断时得到的概念性碎片合成等价物：能起合成子作用的试剂。FGI:FunctionalGroupInterconversion

官能团互换

FGI：把一个官能团转换成另一种官能团。目的：使一种切断成为可能。符号：切断的选择DisconnectionofmonoFunctionalGroup1.SimpleAlcohol选择最稳定的负离子处切断通常情况是没有一个取代基能给出稳定负离子

Howwedo?负离子等价物有了两个好的切断标准：1）合理。2）简单带有两个相同取代基的叔醇=酯+2GrignardNaBH4

只能还原醛，酮。不能还原酯LiAlH4

能还原所有羰基化合物2Derivativesofalcohol涉及H-还原时，实际是FGI遇到上述结构，FGI到醇是一种好的思路Homework3DisconnectionofsimplealkeneAdditionofH2O切断：1）合理。2）简单。3）原料易得4DisconnectionofAromaticKetone将醇切断成羰基化合物和Grignard试剂----第一种主要切割将烯键切断成羰基化合物和Wittig试剂----第二种主要切断将芳香环上脂肪侧链切断---第三种主要切断5ControllingProtection!真麻烦！6DisconnectionofSimpleketoneandAcid7LongChainAlkaneHydrogenationisoneofmaymethod交叉点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苯偶姻反应B)1,2-Diol

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

Comprehensive