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1、STUDYONTHESYNTHESISOF0cFORMYLPYRROLESFROMPYRROLESANDPYRROLE[3,2一C]QUINOLINONEDERIVATIVES4DissertationSubmittedtotheGraduateSchoolofHenanNormalUniversityinPartialFulfillmentoftheRequirementsfortheDegreeofMasterofScienceBy

2、JinglingQianSupervisor:ProfGuishengZhangAssProfZhiguoZhangMay2015ABSTRACTThethesisconsistsofthefollowingtwoaspects:1thesynthesisof0【formylpyrr01esfrom23一dihydro。1Hpyrroles;2thesynthesisofpyrrolo[3,2c]quinolinonederivativ

3、es1Thesynthesisofa—formylpyrrolesq’Formylpyrrolesareoneofthemostimportantfive—memberedheterocycliccompoundspossessingImportantbioactivitiesandimportantintermediatesofsynthesisofpoly。substitutedpyrrolederivativesDevelopme

4、ntofnewpracticalandgreenmethodstosynthesizeq。formylpyrrolesisstillachallengingtaskInthiswork,wediscloseanewtandemdehydrogenation/C2formylmionreactionofl,4,5substituted23dihydro1肛pyrroiesthatise仃ectiVeIycatalyzedbycopper(

5、I)iodide(CuI)inthepresenceoftr訊uoroaceticacid(TFA)anddimethylsulfoxide(DMSO)todirectlygeneratestructuraldiverseO【formylpyrr01esinonep吼inmoderatetogoodyieldsDuringthisreactionDMSOactsasboththecarbonylcarbonsourceandsolven

6、tItwasfoundthatallthesubstrateswithelectronwithdrawin2groupsonpyrroleringunderwentsmoothlyDespitehavingsomelimitations,thistandem’eactionprovidesafacilenewprotocolforthepreparationofstructurallysophisticatedpyrr01ecompou

7、nds2Thesynthesisofpyrrolo[3,2c]quinolinederivativesPyrrolo[3,2’c]quinolinederivativespossessinterestingbiologicalactivities,suchasantlcance‘a(chǎn)ntibacterialactivityetcPyrrolo[3,2一c]quinolinederivativescanbepreparedinseVera】

8、methodsInthisthesis,wedevelopedadirectedCHfunctionalizationand1mramolecularamidearylationfortheefficientconstructionofsubstitutedpyrrolo[3,2‘c]quinolinonesfrom12,3一trisubstitutedpyrrolesinDMSObyusing02asoxldantmthepresen

9、ceofcatalyticCuIItwasalsofoundthataformylpyrrolo[3,2。c]quinolinonescouldbefinallyobtainedintheyieldof21%35%ifthereactiontimewasprolongedThepreliminaryexperimentssuggestedafeasiblemethodtosynthesizea‘formylpyrrolo[3,2。c]q

10、uinolinonesfrom12,3trisubstitutedpyn—olesinonepotwhichprovidesthemeansforfurthermodifyingpyrrolo[3,2c]quinolinones1(EYwolIDS:aformylpyrroles;pyrrolo[3,2cJquinolinonederivatives;Culcatalysis;dimethylsulfoxide(DMSO);formyl

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