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1、2024/9/91 答答辩人：人：XXXXXX导师: : XXXXXX教授教授光催化光催化2-取代苯并取代苯并噻唑的合成及芳的合成及芳烃C-H官能化研究官能化研究New Synthetic Methods for the Preparation of 2-Substituted Benzothiazoles And Photocatalytic Direct C-H Arylation.2024/9/92Contents1. Background2. Research proposal3. Work progress (I, II, III, IV)4. Acknowledgment.2024
2、/9/931.1. Background of Photoredox ChemistryR:genericorganicsubstituentFG:electron-withdrawingfunctionalgroup1. Background Nicewicz,D.A.;MacMillan,D.W.C.Science2008,322,77Hedstrand,D.M.;Kellogg,R.M.Tetrahedron Lett. 1978,19,1255.2024/9/94Dai,C.;Narayanam,J.M.R.;Stephenson,C.R.J.Nat. Chem. 2011,3,140
3、Ischay,M.A.;Anzovino,M.E.;Du,J.;Yoon,T.P.J. Am. Chem. Soc.2008,31,14604.2024/9/951.2. Background of 2-Substituted BenzothiazolesFatty acid amide hydrolase inhibitor Antitumor agentZopolrestat.2024/9/961.2.1. Main SyntheticMethods of 2-Substituted Benzothiazoles 1.Bahrami,K.Khodaei,M.M.J. Org. Chem.2
4、008,73,68352.Yao.S.;Schafer-Hales,K.J.;Belfield,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.
5、Lett.2008,10, 51477.Joyce,L.L.;Batey,R.A.Org. Lett.2009,11,27928.Mu,X.;Zou,J.;Tetrahedron Lett.2005,46,4345.2024/9/97Inamoto,K.;Hasegawa,C.;Hiroya,K.;Doi,T.Org. Lett.2008,10,5147Joyce,L.L.;Batey,R.A.Org. Lett.2009,11,2792.2024/9/982. Research proposal ? ?.2024/9/993.Work progressI. Aerobic Visible-L
6、ight Photoredox RadicalC-H Functionalization: Catalytic Synthesis of 2-Substituted Benzothiazoles.2024/9/910a:HPLCyield;b:Isolatedyield;c:Under5%O2balloon.;d:0.5equivDBUwasused.e:Reactionwascarriedoutindark.f:Underair;g:Under100%O2balloonTable 1. Optimization of Reaction Conditions.2024/9/911Table 2
7、.Synthesisof2-Phenylbenzothiazoles .2024/9/912Table 3.Substitutionsonthe2-Phenylgroup .2024/9/913Scheme 2TheProposedMechanismPhotoredoxundersunlightScheme 1.IntramolecularKineticStudy.2024/9/914II. Heterogeneous Ligand-free Pd/C Catalyzed Synthesis of 2-Substituted Benzothiazoles .2024/9/915Table 1.
8、OptimizationofReactionConditions.2024/9/916Table 2. Synthesis of 2-Arylbenzothiazoles a: Reaction conditions: substrate (1 eq.), Pd/C (2 mol%), rt, N2 atmosphere, 24 hr. b: Isolated yield; c: Pd/C (5 mol%); .17Table 3. Synthesis of 2-Alkylbenzothiazolesb: Isolated yield; c: Pd/C (5 mol%); d: Pd/C (1
9、0 mol%); .2024/9/918III. Transition-Metal-Free Cyclization For the Preparation of 2-Substituted Benzothiazoles.2024/9/919Table 1.OptimizationofReactionConditions.2024/9/920Table 2. Synthesis of 2-Arylbenzothiazoles b:isolatedyield,c:reactiontimeis24h,d:reactiontemperaturewas120C.2024/9/921Table 3. S
10、ynthesis of 2-Alkylbenzothiazolesb:isolatedyield,c:reactiontemperaturewas120C.2024/9/9224. Summary1)visible-lightisthereactiondrivingforce2)molecularoxygenistheterminaloxidant3)C-HFunctionalization1)ligand-free2)roomtemperature3)cantoleratemanyfunctionalgroups1)transition-metal-free2)toleratemanyfun
11、ctionalgroups3)staringmaterialreadilyavailable.IV: Visible-Light Photoredox in Homolytic Aromatic Substitution: Direct Arylation of Arenes with Aryl Halides 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.2010,2,1044Liu,W.;Cao,H.;Zhang,H.;Chung,K.H.;He,C
12、.;Wang,H.;Kwong,F.Y.;Lei,A.J. Am. Chem. Soc.2010,132,16737Shirakawa,E.;Itoh,K.;Higashino,T.;Hayashi,T.J. Am. Chem. Soc.2010,132,15537Liu,W.;Tian,F.;Wang,X.;Yu,H.;Bi,Y. Chem. Commun.2013,49,298324.Nguyen,J.D.;DAmato,E.M.;Narayanam,J.M.R.;Stephenson,C.R.J.Nat. Chem. 2012,4,854Kim,H.;Lee,C.Angew. Chem.
13、 Int. Ed. 2012,51,1230325碘苯的还原电位: -1.59-2.24V, -1.73v(Ir4+ Ir3+*) Versus SCE .Table 1. Optimization of Reaction Conditionsaa:reactionconditions:iodobenzene(0.5mmol),catalyst(0.5mol%),base(3equiv.)inbenzene(3mL),irradiatedundera14Wcompactfluorescentlampirradiationatroomtemperature.b:GCyield;c:freeze-
14、thawdegassed;d:reactionwascarriedoutindark26.Table 2. HAS reactions of aryl iodide with benzenea27.Table 3HAS reactions of aryl bromide with benzeneab: Isolated yield; c: the reaction temperature was at room temperature; d: the reaction temperature was at 35 C; e: the reaction temperature was 80 C;
15、f: the reaction temperature was 90 C g: GC yield.28.Table 4. HAS reactions of aryl halides with arenesa29.Scheme 1. The Proposed Mechanism30.2024/9/931Budn,M.E.;Guastavino,J.F.;Rossi,R.A.Org. Lett.2013,15,1174.OurgroupOrg. Lett. 2013, 15,xxxx，DOI:10.1021/ol400946k.2024/9/932Publications: 1. Aerobic
16、Visible-Light Photoredox Radical Catalytic Synthesis of 2-Substituted Benzothiazoles YannanCheng,JunYang,YueQu,andPixuLi* Org. Lett.2012,14,98101 1.Visible-Light Photoredox in Homolytic Aromatic Substitution: Direct Arylation of Arenes with Aryl Halides YannanCheng,XiangyongGu,andPixuLi* Org. Lett.2
17、013,15,xxxxxxxx Manuscripts in preparation:2.HeterogeneousLigand-freePd/CCatalyzedSynthesisof2-SubstitutedBenzothiazoles3.Transition-Metal-FreeCyclizationForthePreparationof2-SubstitutedBenzothiazoles.2024/9/933Acknowledgment: 本本论文文是是在在我我的的导师XXXXXX教教授授的的精精心心指指导下下完完成成的的，该论文文调研研、选题、撰撰写写到到修修订都都凝凝结着着李李老
18、老师的的很很多多心心血血。在在研研究究生生学学习的的三三年年时光光里里，李李老老师严谨的的治治学学态度度和和科科研研思思维都都深深深深感感染染着着我我，同同时指指引引我我在在科科研研工工作作中中面面对难关关时要要不不抛抛弃弃，不不放放弃弃。他他不不仅亲自自指指导我我的的科科研研工工作作，同同时还让我我独独立立去去探探索索新新课题。他他不不单只只对我我们严格格要要求求，还经常常鼓鼓励励我我们，关关心心我我们的的日日常常生生活活，经常常和和我我们打打成成一一片片去去体体育育锻炼、郊郊游游等等休休闲活活动。所所谓“学学贵得得师，亦，亦贵得友得友”，李老，李老师不不仅是我的良是我的良师更是我的益友。更
19、是我的益友。 深深深深感感谢XXXXXX教教授授在在我我研研究究生生入入学学前前对我我的的指指导，使使我我在在之之后后的的研研究究生生学学习生生活活中中更更加加得得心心应手手。测试中中心心的的老老师给我我的的论文文工工作作提提供供了了大大量量的的协助助，在在此此对他他们的的辛辛勤勤劳动表表示示衷衷心心的的感感谢。感感谢材材化化部部的的领导、资料室、研究生料室、研究生处、图书馆的老的老师们所所给予的予的诸多帮助。多帮助。 还要要感感谢陈XXXX、谷谷XX,XXXXX,XXX等等师兄兄师姐姐们对我我的的扶扶持持与与帮帮助助；感感谢与与我我同同时入入学学XXXXXX的的帮帮助助与与支支持持；感感谢本本课题组的的XXXX、XXXX、XXXX最最后后感感谢我我的的家家人以及其他的人以及其他的亲朋好友朋好友对我学我学业的支持和帮助。的支持和帮助。.2024/9/934Thanks for your attention !.
