硕士论文答辩PPT

2020/4/27,1,答辩人：XXX导师:XXX教授,光催化2-取代苯并噻唑的合成及芳烃C-H官能化研究NewSyntheticMethodsforthePreparationof2-SubstitutedBenzothiazolesAndPhotocatalyticDirectC-HArylation,2020/4/27,2,Contents1.Background2.Researchproposal3.Workprogress(I,II,III,IV)4.Acknowledgment,2020/4/27,3,1.1.BackgroundofPhotoredoxChemistry,R:genericorganicsubstituentFG:electron-withdrawingfunctionalgroup,1.Background,Nicewicz,D.A.;MacMillan,D.W.C.Science2008,322,77,Hedstrand,D.M.;Kellogg,R.M.TetrahedronLett.1978,19,1255,2020/4/27,4,Dai,C.;Narayanam,J.M.R.;Stephenson,C.R.J.Nat.Chem.2011,3,140,Ischay,M.A.;Anzovino,M.E.;Du,J.;Yoon,T.P.J.Am.Chem.Soc.2008,31,14604,2020/4/27,5,1.2.Backgroundof2-SubstitutedBenzothiazoles,Fattyacidamidehydrolaseinhibitor,Antitumoragent,Zopolrestat,2020/4/27,6,1.2.1.MainSyntheticMethodsof2-SubstitutedBenzothiazoles,1.Bahrami,K.Khodaei,M.M.J.Org.Chem.2008,73,68352.Yao.S.;Schafer-Hales,K.J.;Beleld,K.D.Org.Lett.2007,9,56453.Bose,D.S.;Idrees,M.J.Org.Chem.2006,71,82614.Joyce,L.L.;Evindar,G.;Batery,R.A.Chem.Commun.2004,4465.Saha,P.;Ramana,T.;Ali,M.A.;Paul,R.;Punniyamurthy,T.J.Org.Chem.2009,74,87196.Inamoto,K.;Hasegawa,C.;Hiroya,K.;Doi,T.Org.Lett.2008,10,51477.Joyce,L.L.;Batey,R.A.Org.Lett.2009,11,27928.Mu,X.;Zou,J.;TetrahedronLett.2005,46,4345,2020/4/27,7,Inamoto,K.;Hasegawa,C.;Hiroya,K.;Doi,T.Org.Lett.2008,10,5147,Joyce,L.L.;Batey,R.A.Org.Lett.2009,11,2792,2020/4/27,8,2.Researchproposal,?,2020/4/27,9,3.Workprogress,I.AerobicVisible-LightPhotoredoxRadicalC-HFunctionalization:CatalyticSynthesisof2-SubstitutedBenzothiazoles,2020/4/27,10,a:HPLCyield;b:Isolatedyield;c:Under5%O2balloon.;d:0.5equivDBUwasused.e:Reactionwascarriedoutindark.f:Underair;g:Under100%O2balloon,Table1.OptimizationofReactionConditions,2020/4/27,11,Table2.Synthesisof2-Phenylbenzothiazoles,2020/4/27,12,Table3.Substitutionsonthe2-Phenylgroup,2020/4/27,13,Scheme2TheProposedMechanism,Photoredoxundersunlight,Scheme1.IntramolecularKineticStudy,2020/4/27,14,II.HeterogeneousLigand-freePd/CCatalyzedSynthesisof2-SubstitutedBenzothiazoles,2020/4/27,15,Table1.OptimizationofReactionConditions,2020/4/27,16,Table2.Synthesisof2-Arylbenzothiazoles,a:Reactionconditions:substrate(1eq.),Pd/C(2mol%),rt,N2atmosphere,24hr.b:Isolatedyield;c:Pd/C(5mol%);,17,Table3.Synthesisof2-Alkylbenzothiazoles,b:Isolatedyield;c:Pd/C(5mol%);d:Pd/C(10mol%);,2020/4/27,18,III.Transition-Metal-FreeCyclizationForthePreparationof2-SubstitutedBenzothiazoles,2020/4/27,19,Table1.OptimizationofReactionConditions,2020/4/27,20,Table2.Synthesisof2-Arylbenzothiazoles,b:isolatedyield,c:reactiontimeis24h,d:reactiontemperaturewas120C,2020/4/27,21,Table3.Synthesisof2-Alkylbenzothiazoles,b:isolatedyield,c:reactiontemperaturewas120C,2020/4/27,22,4.Summary,1)visible-lightisthereactiondrivingforce2)molecularoxygenistheterminaloxidant3)C-HFunctionalization,1)ligand-free2)roomtemperature3)cantoleratemanyfunctionalgroups,1)transition-metal-free2)toleratemanyfunctionalgroups3)staringmaterialreadilyavailable,IV:Visible-LightPhotoredoxinHomolyticAromaticSubstitution:DirectArylationofAreneswithArylHalides,23,Sun,C.L.;Li,H.;Yu,D.G.;Yu,M.;Zhou,X.;Lu,X.Y.;Huang,K.;Zheng,S.F.;Li,B.J.;Shi,Z.J.Nat.Chem.2010,2,1044,Liu,W.;Cao,H.;Zhang,H.;Chung,K.H.;He,C.;Wang,H.;Kwong,F.Y.;Lei,A.J.Am.Chem.Soc.2010,132,16737,Shirakawa,E.;Itoh,K.;Higashino,T.;Hayashi,T.J.Am.Chem.Soc.2010,132,15537,Liu,W.;Tian,F.;Wang,X.;Yu,H.;Bi,Y.Chem.Commun.2013,49,2983,24,Nguyen,J.D.;DAmato,E.M.;Narayanam,J.M.R.;Stephenson,C.R.J.Nat.Chem.2012,4,854,Kim,H.;Lee,C.Angew.Chem.Int.Ed.2012,51,12303,25,碘苯的还原电位:-1.59-2.24V,-1.73v(Ir4+Ir3+*)VersusSCE,Table1.OptimizationofReactionConditionsa,a:reactionconditions:iodobenzene(0.5mmol),catalyst(0.5mol%),base(3equiv.)inbenzene(3mL),irradiatedundera14Wcompactfluorescentlampirradiationatroomtemperature.b:GCyield;c:freeze-thawdegassed;d:reactionwascarriedoutindark,26,Table2.HASreactionsofaryliodidewithbenzenea,27,Table3HASreactionsofarylbromidewithbenzenea,b:Isolatedyield;c:thereactiontemperaturewasatroomtemperature;d:thereactiontemperaturewasat35C;e:thereactiontemperaturewas80C;f:thereactiontemperaturewas90Cg:GCyield.,28,Table4.HASreactionsofarylhalideswitharenesa,29,Scheme1.TheProposedMechanism,30,2020/4/27,31,Budn,M.E.;Guastavino,J.F.;Rossi,R.A.Org.Lett.2013,15,1174.,Ourgroup,Org.Lett.2013,15,xxxx，DOI:10.1021/ol400946k,2020/4/27,32,Publications:1.AerobicVisible-LightPhotoredoxRadicalCatalyticSynthesisof2-SubstitutedBenzothiazolesYannanCheng,JunYang,YueQu,andPixuLi*Org.Lett.2012,14,98101Visible-LightPhotoredoxinHomolyticAromaticSubstitution:DirectArylationofAreneswithArylHalidesYannanCheng,XiangyongGu,andPixuLi*Org.Lett.2013,15,xxxxxxxxManuscriptsinpreparation:2.HeterogeneousLigand-freePd/CCatalyzedSynthesisof2-SubstitutedBenzothiazoles3.Transition-Metal-FreeCyclizationForthePreparationof2-SubstitutedBenzothiazoles,2020/4/27,33,Acknowledgment:,本论文是在我的导师XXX教授的精心指导下完成的，该论文调研、选题、撰写到修订都凝结着李老师的很多心血。在研究生学习的三年时光里，李老师严谨的治学态度和科研思维都深深感染着我，同时指引我在科研工作中面对难关时要不抛弃，不放弃。他不仅亲自指导我的科研工作，同时还让我独立去探索新课题。他不单只对我们严格要求，还经常鼓励我们，关心我们的日常生活，经常和我们打成一片去体育锻炼、郊游等休闲活动。所谓“学贵得师，亦贵得友”，李老