过渡金属催化叠氮与炔的环化反应及其在有机合成中的应用-化学 有机化学专业论文.docxVIP

兰州大学博士学位论文牛雁宁AbstractAzideisakindofveryimportantorganicintermediate．Itcanreactwithorganiccompoundstoaffordmanynitrogen—containingcompounds．Theazide-alkynecyclizationreactionhavebeenreceivedmuchattentioninrecentyearsandwidelyfoundapplicationinmanyfields．Inthispaper,weareinterestedinthetransitionmetal—catalyzedazideandalkynecyclizationreactionanditsapplicationinorganicsynthesis，whichincludingthefollowing：Inthefhstchapter，wehavereviewedtherecentstudiesabouttheazide—alkynecyclizationreactionanditsapplication．WehavesummarizedtheHuigenreaction,suchasthetraditionalHuisgenreaction，Cu(1)-catalyzedHuisgenreaction，andothermetals-catalyzedHuisgenreactiontosynthsizeavarietyofsubsititutedtriazoles．Wehavealsosummarizedsulfonylazideandalkyne—involvedmulti—componentreactions，andintramolecularazide-alkynecyclizationreactions．Inthesereactions，Cu(1)一catalyzedazideandalkynecycloadditionreactions(CttAAC)havebeenwidelyusedinmanyfields，andwealsohavegivenabriefsummaryonitsapplication．InChapterII，First，wehavereviewdthestudiesonthethechiralaminoalcohols，whichhadbeenusedintheborane—mediatedreductionofprochiralketones．Wehavesynthesized1,2，3-triazole-functionalized，C3-symmetricchiralaminoalcoholcatalystsv／aCuAACreaction．Thosecatalystshavebeenusedintheborane-mediatedreductionofprochiralketones．Theresultsshowedthatthecatalystshadgoodcatalyticactivity,anditcouldeasilyprecipitateoutfromthereac．tionmixtureandbereusedafterasimplewashinganddrying．Thecatalystcanbereusedfourtimes，withoutobviousdecreaseofcatalyticactivity．InChapterIII，wehavedevelopedtheAg-catalyzedintramolecularorganicazideandalkynecyclizationtosynthesizeof1,3一disubstitutedisoquinolinesornon-substitutedisoquinolines．FirStlywehavereviewedtherecentstuidesonisoquinolinesynthesis．Sencondly,thereactionconditionswereoptimized，andthescopeofthisreactionWasinvestigated．Thirdly,wehavealsodiscussedtheelectronocⅡ兰州大学博士学位论文牛雁宁effectofsubstituentsonthearomaticringandproposedaresonablereactionmechanism．Theresultsshowedthatthesubstitutedisoquinolinecould