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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 蔡蘊明(Yeun-Min Tsai) | |
| dc.contributor.author | Jen-Yu Hsu | en |
| dc.contributor.author | 徐仁佑 | zh_TW |
| dc.date.accessioned | 2021-06-13T15:19:21Z | - |
| dc.date.available | 2008-07-26 | |
| dc.date.copyright | 2008-07-26 | |
| dc.date.issued | 2008 | |
| dc.date.submitted | 2008-07-24 | |
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| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/37109 | - |
| dc.description.abstract | 本實驗室之前針對矽基酮與烯基自由基環化反應的研究，顯示出此類化合物具有開發連繼性環化反應的可能。烯基自由基環化後所得到β-矽基烷氧自由基，經過Brook重排，產生因共振而穩定的烯丙基自由基。此系統最特殊的地方在於雙鍵的存在，自由基中間體可以透過共振使得三號碳的位置上具有自由基性質。我們利用這種特性，希望將此形式的反應發展為連繼性環化反應。
我們的構想是利用炔基做為自由基受體，利用三號碳所具有的自由基性質，進行第二次環化反應，架構出雙環化合物。本文設計出兩種類型的環化前驅物進行研究。 | zh_TW |
| dc.description.abstract | According to previous research in our laboratory, cyclizations of acylsilanes with vinyl radicals have been studied. This process involved intramolecular free radical cyclizations of a vinyl radical to the carbonyl group of acylsilane to give a β-silyl alkoxy radical. This radical then undergoes a radical Brook rearrangement to afford an α-silyloxy radical. Due to the presence of the vinyl group, this α-silyloxy radical is also an allylic radical. Finally, hydrogen abstraction occurs at the γ-position of this allylic system to give an enol silyl ether. Generally, 1,5-exo-cyclizations are more efficient than 1,6-exo-cyclizations.
In this research we exploited this system further in the context of tandem radical cyclizations. We have constructed two systems in which the intermediate allylic radicals are trapped intramolecularly at the γ-position by radicalphilic groups. Specifically, we have synthesized acylsilanes with vinyl iodide tethered to an alkynyl functional group. The scope and limitations of this type of tandem cyclizations were studied. | en |
| dc.description.provenance | Made available in DSpace on 2021-06-13T15:19:21Z (GMT). No. of bitstreams: 1 ntu-97-R95223016-1.pdf: 5474156 bytes, checksum: f7bd3a6e9d170cd3b37590aee53fc769 (MD5) Previous issue date: 2008 | en |
| dc.description.tableofcontents | Content 1
Chinese Abstract 2 English Abstract 3 Abbreviation 4 Content of Tables 6 1. Introduction 7 2. Results and Discussion 12 2.1 The type I tandem cyclization system formation of [3.3.0] bicyclic skeleton 12 2.2 The type I tandem cyclization system: formation of [3.4.0] bicyclic skeleton 22 2.3 The type II tandem cyclization system: formation of [3.3.0] bicyclic skeleton 29 3. Conclusion 44 4. Experimental Section 46 5. References and Notes 74 Appendix: 1H and 13C NMR spectra 77 | |
| dc.language.iso | en | |
| dc.subject | 自由基 | zh_TW |
| dc.subject | 丙烯基自由基 | zh_TW |
| dc.subject | 矽基酮 | zh_TW |
| dc.subject | 環化反應 | zh_TW |
| dc.subject | cyclization | en |
| dc.subject | vinyl radical | en |
| dc.subject | acylsilane | en |
| dc.subject | radical | en |
| dc.title | 烯基自由基與矽基酮進行自由基連繼性環化反應的研究 | zh_TW |
| dc.title | The Study of Tandem Radical Cyclization of Vinyl Radical with Acylsilanes | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 96-2 | |
| dc.description.degree | 碩士 | |
| dc.contributor.oralexamcommittee | 楊吉水(Jye-Shane Yang),邱勝賢(Sheng-Hsien Chiu) | |
| dc.subject.keyword | 自由基,環化反應,矽基酮,丙烯基自由基, | zh_TW |
| dc.subject.keyword | radical,cyclization,acylsilane,vinyl radical, | en |
| dc.relation.page | 117 | |
| dc.rights.note | 有償授權 | |
| dc.date.accepted | 2008-07-24 | |
| dc.contributor.author-college | 理學院 | zh_TW |
| dc.contributor.author-dept | 化學研究所 | zh_TW |
| 顯示於系所單位： | 化學系 | |
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