DC Field | Value | Language |
---|---|---|
dc.contributor.advisor | Pak, Chwang-Siek | - |
dc.contributor.advisor | Kim, Yong-Hae | - |
dc.contributor.advisor | 박창식 | - |
dc.contributor.advisor | 김용해 | - |
dc.contributor.author | Kim, Sung-Kee | - |
dc.contributor.author | 김성기 | - |
dc.date.accessioned | 2011-12-13T04:25:47Z | - |
dc.date.available | 2011-12-13T04:25:47Z | - |
dc.date.issued | 1991 | - |
dc.identifier.uri | http://library.kaist.ac.kr/search/detail/view.do?bibCtrlNo=61617&flag=dissertation | - |
dc.identifier.uri | http://hdl.handle.net/10203/31354 | - |
dc.description | 학위논문(박사) - 한국과학기술원 : 화학과, 1991.8, [ vii, 133 p. ] | - |
dc.description.abstract | Cyclohept-3-3nones were prepared in four to five steps starting from cyclopentanone sily enol ether in high overall yields(42-75\%). Silyl enol ethers of cyclopentanones were converted to dichlorobicyclo [3.2.0] heptanones(75-88\%) via [2+2] cycloaddition with dichloroketene generated from trichloroacetyl chloride. Dechlorination of the dichlorobicyclic ketones was performed by treatment with tributyltin hydride in the presence of AIBN to give bicyclic ketones(89-94\%). The ketones were either reduced with sodium borohydride or treated with methylmagnesium bromide to give bicyclic secondary or tertiary alcohols(95-98\%). The secondary alcohols were subjected to mesylation ($CH_3SO_2Cl$, $Et_3N$/DCM) and fragmentation (n-$Bu_4NF$/THF) condition to give cyclohpt-3-enones(59-64\%). On the other hand the tertiary bicyclic alcohols underwent fragmentation spontaneously during mesylation condition to give the corresponding cyclohept-3-enones almost quatitatively. All the cyclohept-3-enones were converted into the corresponding cyclohept-2-enones quatitatively by treatment with p-TsOH. Similary, thermal [2+2]cycloaddition of silyl enol ethers with dithisubstituted ketene gave the corresponding cycloadducts. However, when the cycloadducts were treated with $Bu_4NF$, $C_1$-$C_7$ bond cleavage occurred exclusively resulting diketones in almost quantitative yield. 6-Methylbicyclo [5.3.0] dec-10-en-2-one having trans configuration between $C_6$-methyl and $C_7$-proton was synthesized by applying the above methodology for cycloheptenone synthesis. The 5-methyl-1-(trimethyl siloxy) bicyclo [3.2.0]heptanone was treated with Grignard reagent of 2-(2-bromoethyl)-1,3-dioxane, and subsequent fragmentation produced the corresponding cyclohept-3-enone. Stereoselective hydrogenation of cycloheptenone was achieved in the presence of rodium on alumina affording a stereoisomer mixture of cis and trans(15:1). Acid catalyzed cyclization of cycloheptanone derivative was carried out by Hea... | eng |
dc.language | eng | - |
dc.publisher | 한국과학기술원 | - |
dc.title | (A) convenient method for the preparation of cyclo-heptenones | - |
dc.title.alternative | 시클로 헵테논류의 간편한 제조방법 및 이를 이용한 히드로 아줄렌 골격의 합성 | - |
dc.type | Thesis(Ph.D) | - |
dc.identifier.CNRN | 61617/325007 | - |
dc.description.department | 한국과학기술원 : 화학과, | - |
dc.identifier.uid | 000835515 | - |
dc.contributor.localauthor | Pak, Chwang-Siek | - |
dc.contributor.localauthor | Kim, Yong-Hae | - |
dc.contributor.localauthor | 박창식 | - |
dc.contributor.localauthor | 김용해 | - |
dc.title.subtitle | its application to hydroazulene skeletons | - |
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