Studies on new pathways to 1,3-Diyl and their application to triquinane synthesis = 1,3-다이일의 새로운 합성 방법들과 트리퀴난 합성에의 응용에 관한 연구

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Development of new pathways to 1,3-diyl for cycloaddition reaction to construct various polyquinane frameworks has been studied. The intramolecular [2+3] cycloaddition reaction of the 1,3-trimethylenemethane(TMM) diyl generated from the intramolecular cyclopropanation reaction of alkylidene carbene produced linearly, angularly fused triquinanes and tetaquinanes regio- and stereoselectively. This method provides a good synthetic strategy to construct polyquinane skeletons. However, it exhibits the several disadvantages such as 1,2-shift of alkylidene carbene and relatively low product yield. Therefore, alternative generation method of 1,3-diyl was needed to apply for the construction of polyquinane skeleton. A new efficient way to generate 1,3-trimethylenemethane(TMM) diyl was developed with allene and N-aziridinylimine or with allene and N-tosylhydrazone sodium salt. This synthetic strategy was successfully utilized in [2+3] cycloaddition reaction with olefin in high yield. The novel one pot sequential transformation of thermally labile pyrazole obtained through [2+3] cycloaddition reaction of diazoalkane with allene produced 1,3-trimethylenemethane(TMM) diyl and the generated diyl was trapped by olefin to form polyquinane framework. Total Synthesis of dl-pentalenene, angular triquinane natural product, was successful through 11 steps from (E)-2-methylhept-5-en-1-ol. Triquinane core structure was assembled by thermolysis of allenyl N-tosylhydrazone sodium salt.
Advisors
Lee, Hee-Yoonresearcher이희윤researcher
Description
한국과학기술원 : 화학과,
Publisher
한국과학기술원
Issue Date
2009
Identifier
309371/325007  / 020045858
Language
eng
Description

학위논문(박사) - 한국과학기술원 : 화학과, 2009.2, [ v, 292 p. ]

Keywords

1,3-diyl; linear triquinane; angular triquinane; tetraquinane; pentalenene; 1,3-다이일; 선형 트리퀴난; 각형 트리퀴난; 테트라퀴난; 펜탈레넨; 1,3-diyl; linear triquinane; angular triquinane; tetraquinane; pentalenene; 1,3-다이일; 선형 트리퀴난; 각형 트리퀴난; 테트라퀴난; 펜탈레넨

URI
http://hdl.handle.net/10203/31720
Link
http://library.kaist.ac.kr/search/detail/view.do?bibCtrlNo=309371&flag=dissertation
Appears in Collection
CH-Theses_Ph.D.(박사논문)
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