Transition metal-catalyzed intramolecular C-H functionalization = 전이금속 촉매반응을 이용한 분자 내 탄소-수소 결합 활성화반응에 관한 연구

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Trasition metal-catalyzed C−H functionalization has been extensively investigated to prepare complex molecules as an alternative to the conventional cross-coupling, where pre-functionalized starting materials were required. $Cp^*Ir$ and $Cp^*Rh$ complexes have been utilized in development of C−N and C−C bond construction with chelation-assisted C−H activation. Meanwhile, due to the unstability of metal-nitrenoid and metal-carbenoid, development of efficient reaction using these intermediacy has to be surmounted. In this context, herein I describe the development of C−N and C−C bond forming processes using $Cp^*M$ (M = Rh or Ir) system. First, I have developed $Cp^*Rh(III)$-catalyzed intramolecular amido transfer as an efficient route to nitrogen-containing macrocycles for the first time. In contrast to the well-studied the conventional C−H insertion approach, which is able to synthesize 5- to 7-membered medium-sized rings, facile generation of rhodacycles and then imido intermediates was readily achieved from ketoximes tethered with azides. While substrates bearing aryl azides underwent a monomeric ring formation in high yields, a dimeric double cyclization took place exclusively with alkyl azide-tethered ketoximes affording up to 36-membered azamacrocyclic products. Second, a new catalytic procedure for carbon-carbon bond formation has been developed using bidentate LX type ligand based $Cp^*Ir(III)$-carbenoid system. Although metal-carbenoid transfer reaction has been well studied to achieve a wide range of organic transformations, the development of $Cp^*Ir(III)$-carbenoid transfer is still in infancy owing to the lack of solid mechanistic understanding of these putative intermediates. In this study, $Cp^*Ir$-catalyzed carbene transfer reaction was developed using diazo compounds as a carbene precursor with a high turnover number under mild reaction conditions.
Advisors
Chang, Sukbokresearcher장석복researcher
Description
한국과학기술원 :화학과,
Publisher
한국과학기술원
Issue Date
2019
Identifier
325007
Language
eng
Description

학위논문(박사) - 한국과학기술원 : 화학과, 2019.2,[iv, 63 p. :]

Keywords

C-H Activation▼aintramolecular reaction▼anitrenoid▼aazides▼acarbenoid▼adiazo compounds; 탄소-수소 결합 활성▼a분자 내 반응▼a나이트렌▼a아자이드▼a카벤▼a다이아조 화합물

URI
http://hdl.handle.net/10203/265499
Link
http://library.kaist.ac.kr/search/detail/view.do?bibCtrlNo=842464&flag=dissertation
Appears in Collection
CH-Theses_Ph.D.(박사논문)
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