DC Field | Value | Language |
---|---|---|
dc.contributor.advisor | Lee, Hee-Yoon | - |
dc.contributor.advisor | 이희윤 | - |
dc.contributor.author | Lee, Se-Jin | - |
dc.contributor.author | 이세진 | - |
dc.date.accessioned | 2011-12-13T04:29:57Z | - |
dc.date.available | 2011-12-13T04:29:57Z | - |
dc.date.issued | 2004 | - |
dc.identifier.uri | http://library.kaist.ac.kr/search/detail/view.do?bibCtrlNo=237516&flag=dissertation | - |
dc.identifier.uri | http://hdl.handle.net/10203/31623 | - |
dc.description | 학위논문(박사) - 한국과학기술원 : 화학과, 2004.2, [ iii, 145 p. ] | - |
dc.description.abstract | Development of new synthetic methodologies and their applications to the total synthesis of natural products were studied. In the course of synthesis of tricyclo-[4.3.2.$0^{1,5}$] undecane structure, unusual 6-exo radical cyclization was observed. Most of 2,2-disubstituted cyclopentene derivatives cyclized to produce tricyclo-[4.3.2.$0^{1,5}$] undecane through radical reaction sequence, which involved cyclopropyl methyl radical mediated rearrangement. However, in the case of 146a, unusual 6-exo-radical cyclization proceeded due to stereochemistry of secondary hydroxyl group. Tricyclic 151, prepared from β-keto ester 136, was used as a key intermediate for the total synthesis of Nopsan-4-ol. 151 was converted to Nopsan-4-ol by introduction of methyl group via 1,4-addition at C-6, methylation at C-4 position, and stereoselective reduction of olefin. Synthetic method used in the construction of tricyclo-[4.3.2.$0^{1,5}$] undecane was also applied to the total synthesis of Delnudine. BC-ring of Delnudine was prepared through that radical cyclization and rearrangement. After manipulation of functional groups of B-ring, A-ring of Delnudine was prepared through a regioselective alkylidene carbene C-H insertion derived from alkylation of trimethylsilyl-diazomethyl lithium followed by Peterson olefination and α -elimination, and then ozonolysis followed by aldol condensation of resulting cyclopentene. Some manipulations of A-ring were studied to introduce a functional group on unactivated C-18 position. A noteworthy aspect of this synthesis is a one-pot construction of tricyclic ring system. | eng |
dc.language | eng | - |
dc.publisher | 한국과학기술원 | - |
dc.subject | RADICAL | - |
dc.subject | TOTAL SYNTHESIS | - |
dc.subject | DELNUDINE | - |
dc.subject | NOPSAN-4-OL | - |
dc.subject | CYCLIZATION REACTION | - |
dc.subject | 고리화반응 | - |
dc.subject | 라디칼 | - |
dc.subject | 전합성 | - |
dc.subject | 델누딘 | - |
dc.subject | 놉산-4-올 | - |
dc.title | Synthetic studies toward total synthesis of Nopsan-4-ol and Delnudine | - |
dc.title.alternative | 놉산-4-올과 델누딘의 전합성에 관한 연구 | - |
dc.type | Thesis(Ph.D) | - |
dc.identifier.CNRN | 237516/325007 | - |
dc.description.department | 한국과학기술원 : 화학과, | - |
dc.identifier.uid | 000975273 | - |
dc.contributor.localauthor | Lee, Hee-Yoon | - |
dc.contributor.localauthor | 이희윤 | - |
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