Synthesis of polyquinane natural products using the tandem radical cyclizations of aziridinylimine = 아지리디닐이민의 연속적인 라디칼 고리화를 이용한 폴리퀴난계의 천연물의 합성

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Radical reaction of N-aziridinylimines generated 5- and 6-membered ring radicals from acyclic radical precursors. Based on this finding, consecutive carbon-carbon bond formation could be achieved and this approach turned out to be very effective to form quarternary carbon centers in a single synthetic operation. This consecutive carbon-carbon bond formation approach was applied to synthesize naturally occurring sesquiterpenes such as modhephene, cedranoids, and quadrone. Racemic modhephene having [3.3.3.0] propellane skeleton was synthesized from readily available $\alpha$,$\alpha$-disubstituted cyclopentanone aziridinylimine using the tandem radical cyclization of N-aziridinylimine, demonstrating the efficiency and usefulness of consecutive carbon-carbon bond formation approach. Furthermore, the cyclization proceeded in a stereoselective manner. The present approach could be successfully applied to construct [5.3.1.$0^1.5$] and [6.2.1.$0^1.5$] skeletons,which consisted of naturally occurring cedranoids and prelacinan-7-ol, respectively. Similarly, cedranoids such as cedrene, cedrone, and cedrol could be efficiently synthesized via tandem radical cyclization of N-aziridinylimines. The present synthesis was much simpler and more efficient than previously reported synthetic methods. Synthetic studies of silphinene and quadrone were investigated. The key intermediates were prepared in high yields. However, radical cyclizations did not give the desired products and the reasons for the failure are unclear at the present.
Advisors
Kim, Sung-Gakresearcher김성각researcher
Description
한국과학기술원 : 화학과,
Publisher
한국과학기술원
Issue Date
1997
Identifier
128466/325007 / 000945803
Language
eng
Description

학위논문(박사) - 한국과학기술원 : 화학과, 1997.8, [ iii, 186 p. ]

Keywords

Quadrone; Cedrene; Cedrole; Cedrone; Cedranoid; Modhephene; Polyquinane; Tandem radical cyclization; Aziridinylimine; Silphinene; 씰피넨; 쿼드론; 쎄드론; 쎄드롤; 쎄드론; 쎄드라노이드; 아지리디닐이민; 연속적인 라디칼 고리화; 폴리퀴난; 마드헤펜

URI
http://hdl.handle.net/10203/31467
Link
http://library.kaist.ac.kr/search/detail/view.do?bibCtrlNo=128466&flag=dissertation
Appears in Collection
CH-Theses_Ph.D.(박사논문)
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