Studies of C-C and C-N bond forming reactions with aromatic compounds containing directing groups = 지향기를 가지는 벤젠 유도체의 탄소-탄소, 탄소-질소 결합 형성반응에 관한 연구

Cited 0 time in webofscience Cited 0 time in scopus
  • Hit : 525
  • Download : 0
1. Ruthenium-Catalyzed Direct C-H Amidation of Arenes Including Weakly Coordinating Aromatic Ketones The ruthenium-catalyzed direct $sp^2$ C-H amidation of arenes with using sulfonyl azides as the amino source is presented. Under mild conditions without external oxidants, molecular nitrogen is found to be a sole by-product generated from azide. Research on amidation of arenes with various directing groups was conducted to show that wide range of arene substrates bearing pyridyl and amide directing groups were readily amidated. In addition, weakly coordinating ketone directing groups were also applicable to our amidation reactions to provide ortho-amino aryl ketones. This ortho-amino aryl ketones can be useful synthetic unit for the synthesis of biologically active heterocycles. 2. Complete Switch of Selectivity in the C-H Alkenylation and Hydroarylation Catalyzed by Iridium : The Role of Directing Groups $Cp^*$ Ir(III)-catalyzed C-H alkenylation and hydroarylation were studied to find the complete switch of the product-selectivity on the type of directing groups under the same reaction conditions. In our study, directing groups of N-chelator afforded hydroarylated products while directing groups containing carbonyl groups of O-chelator afforded alkenylated products. On the basis of mechanistic studies, we proposed that the origin of product distribution can be correlated to the efficiency of attaining syn-coplanarity of olefin inserted 7-membered iridacycles during the β-H elimination. Computational studies support that the degree of flexibility of this 7-membered key intermediate determines the efficiency of the β-H elimination, and this flexibility is closely related to bond characteristics between Ir center and heteroatom in directing group and the initial iridacycle geometry with each type of directing group.
Advisors
Chang, Sukbokresearcher장석복researcher
Description
한국과학기술원 :화학과,
Publisher
한국과학기술원
Issue Date
2016
Identifier
325007
Language
eng
Description

학위논문(박사) - 한국과학기술원 : 화학과, 2016.2 ,[iii, 110 p. :]

Keywords

C-H bond activation; directing-group; amidation; alkenylation; hydroarylation; 탄소-수소 결합 활성; 지향기; 탄소-질소 결합; 탄소-탄소 결합; 메커니즘

URI
http://hdl.handle.net/10203/222495
Link
http://library.kaist.ac.kr/search/detail/view.do?bibCtrlNo=648311&flag=dissertation
Appears in Collection
CH-Theses_Ph.D.(박사논문)
Files in This Item
There are no files associated with this item.

qr_code

  • mendeley

    citeulike


rss_1.0 rss_2.0 atom_1.0