不对称合成反应.pptVIP

不对称合成反应;手性：

指一个物体与其镜像不重合;2021/4/9;2021/4/9;2021/4/9;手性是自然界的基本属性;;内容;不对称合成;手性分子的费歇尔命名规则;Cahn-Ingold-Prelog命名规则;不对称和非对称;对映体和非对映体;(e.e.)和(d.e.);潜手性面，Re和Si面;二、手性的重要性;手性药物;2、两种对映体药性相反;3、其中一种有毒或引起严重副反应;手性农药;其他领域;海葵毒素;三、手性的发展历史;In1894?，HermannEmilFischer?outlinedtheconceptof?asymmetricinduction;inwhichhecorrectlyascribedselectivetheformationof?D-glucosebyplantstobeduetotheinfluenceofopticallyactivesubstanceswithinchlorophyll.Fischeralsosuccessfullyperformedwhatwouldnowberegardedasthefirstexampleofenantioselectivesynthesis,byenantioselectivelyelongatingsugarsviaaprocesswhichwouldeventuallybecomethe?Kiliani–Fischersynthesis.;However,thefirstenantioselectivesynthesisisoftenattributedtoWillyMarckwald;whoin1904describedtheenantioselective?decarboxylation?ofthe?malonicacid?2-ethyl-2-methylmalonicacid,mediatedby?brucine.;1905–1965;Itwasnotuntilthe1950sthatmajorprogressreallybegan.Driveninpartbychemistssuchas?R.B.Woodward?and?VladimirPrelog?butalsobythedevelopmentofnewtechniques.Thefirstofthesewas?XrayCrystallography,whichwasusedtodeterminethe?absoluteconfiguration?ofanorganiccompoundby?JohannesBijvoet?in1951.?ChiralchromatographywasintroducedayearlaterbyDalgliesh,whoused?paperchromatography?toseparatechiralaminoacids.?AlthoughDalglieshwasnotthefirsttoobservesuchseparations,hecorrectlyattributedtheseparationofenantiomerstodifferentialretentionbythechiralcellulose.Thiswasexpandeduponin1960,whenKlemandReedfirstreportedtheuseofchirally-modifiedsilicagelforchiralHPLC?chromatographicseparation.;Thalidomide;since1965;Metalcatalysedenantioselectivesynthesiswaspioneeredby?WilliamS.Knowles,?RyōjiNoyori?and?K.BarrySharpless;forwhichtheywouldreceivethe2001NobelPrizeinChemistry.KnowlesandNoyoribeganwiththedevelopmentof?asymmetrichydrogenation,whichtheydevelopedindepend