Development of iridium-catalyzed oxidative C-H arylation reactions이리듐 촉매의 탄소-수소 결합 활성화를 통한 산화성 아릴화 반응에 대한 연구

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dc.contributor.advisorChang, Sukbok-
dc.contributor.advisor장석복-
dc.contributor.authorShin, Kwangmin-
dc.contributor.author신광민-
dc.date.accessioned2018-05-23T19:39:36Z-
dc.date.available2018-05-23T19:39:36Z-
dc.date.issued2017-
dc.identifier.urihttp://library.kaist.ac.kr/search/detail/view.do?bibCtrlNo=675882&flag=dissertationen_US
dc.identifier.urihttp://hdl.handle.net/10203/242153-
dc.description학위논문(박사) - 한국과학기술원 : 화학과, 2017.2,[iv, 76 p. :]-
dc.description.abstractIn contrast to the well-studied stoichiometric cyclometalation of half-sandwich iridium(III)-complexes with chelation group containing arenes via C-H cleavage, the development of iridium(III)-catalyzed direct C-H functionalization is still in infancy and the reported catalytic procedures are largely limited to C-N bond formation. In this context, herein we describe the development of iridium(III)-catalyzed oxidative C-H arylation reactions. First, we have developed $Cp^\ast$Ir(III)-catalyzed mild and external oxidant free C-H arylation of arenes and alkenes using aryldiazonium salts as both an aryl precursor and an oxidant via $C-N_2$ bond cleavage. A series of mechanistic studies disclosed that the reaction proceeds via the formation of an Ir(V)-aryl intermediate, which is proposed to be the turnover-limiting step. Synthetic utility of the developed arylation procedure was also demonstrated for the (Z)-selective arylation of enamides and C8-selective arylation of quinoline N-oxides. Second, $Cp^\ast$Ir(III)-catalyzed cross-coupling of C($sp^2$)-H bonds with arylsilanes, aryl nucleophiles, has also been developed. This arylation procedure clearly demonstrates that $Cp^\ast$Ir(III)-catalyst system can mediate the facile carbon-aryl bond formation under ambient reaction conditions in the presence of an oxidant. In addition, this is the first example of the iridium(III)-catalyzed oxidative C-H arylation being compatible with an external oxidant. Mechanistic investigations disclosed that either in-situ generated copper- or silver-aryl species might be involved in the transmetalation step, leading to the formation of isolable iridium(III)-aryl complex. In addition, it was also proved that a catalytic cycle involves the formation of a high-valent iridium-aryl species. The arylation proceeded smoothly over a range of benzamides and enamides.-
dc.languageeng-
dc.publisher한국과학기술원-
dc.subjectC-H activation-
dc.subjectoxidative C-H arylation-
dc.subjectaryldiazonium salts-
dc.subjectarylsilanes-
dc.subject이리듐 촉매 시스템-
dc.subject탄소-수소 결합 활성-
dc.subject산화성 아릴화 반응-
dc.subject아릴 다이아조늄 염-
dc.subject아릴 실레인-
dc.titleDevelopment of iridium-catalyzed oxidative C-H arylation reactions-
dc.title.alternative이리듐 촉매의 탄소-수소 결합 활성화를 통한 산화성 아릴화 반응에 대한 연구-
dc.typeThesis(Ph.D)-
dc.identifier.CNRN325007-
dc.description.department한국과학기술원 :화학과,-
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CH-Theses_Ph.D.(박사논문)
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